On 24 April 2014, Poroshenko visited Luhansk, at the time not controlled by Ukrainian authorities. Just like previously in Crimea he was met by a blockade of hundreds of pro-Russian locals at Luhansk Airport. Poroshenko later claimed: "When I traveled to Luhansk Oblast, my car was fired at and there was an attempt to take our entire group hostage."
Following the 2014 Ukrainian revolution and the resulting removal of Viktor Yanukovych from the office of President of Ukraine, new presidential elections were scheduled to take place on 25 May 2014. In pre-election polls from March 2014, Poroshenko garnered the most support of all the prospective candidates, with one poll conducted by SOCIS giving him a rating of over 40%. On 29 March he stated that he would run for president; at the same time Vitali Klitschko left the presidential contest, choosing to support Poroshenko's bid.
When it became clear he had won the election on election day evening (on 25 May 2014) Poroshenko announced "My first presidential trip will be to Donbas", where armed pro-Russian rebels had declared the separatist republics Donetsk People's Republic and Luhansk People's Republic and control a large part of the region. Poroshenko also vowed to continue the military operations by the Ukrainian government forces to end the armed insurgency claiming: "The anti-terrorist operation cannot and should not last two or three months. It should and will last hours." He compared the armed pro-Russian rebels to Somali pirates. Poroshenko also called for negotiations with Russia in the presence of international intermediaries. Russia responded by saying it did not need an intermediary in its bilateral relations with Ukraine. As president-elect, Poroshenko promised to return Crimea, which was annexed by Russia in March 2014. He also vowed to hold new parliamentary elections in 2014.
Poroshenko was inaugurated in the Verkhovna Rada (parliament) on 7 June 2014. In his inaugural address he stressed that Ukraine would not give up Crimea and stressed the unity of Ukraine. He promised an amnesty "for those who do not have blood on their hands" to the separatist and pro-Russia insurgents of the 2014 pro-Russian conflict in Ukraine and to the Ukrainian nationalist groups that oppose them, but added: "Talking to gangsters and killers is not our path". He also called for early regional elections in Eastern Ukraine. Poroshenko also stated that he would sign the economic part of the Ukraine–European Union Association Agreement and that this was the first step towards full Ukrainian EU Membership. During the speech he stated he saw "Ukrainian as the only state language" but also spoke of the "guarantees [of] the unhindered development of Russian and all the other languages". Part of the speech was in Russian.
On 25 August 2014, Poroshenko called a snap election to the Verkhovna Rada (Ukraine's parliament), to be held 26 October 2014. According to him this was necessary "to purify the Rada of the mainstay of [former president] Viktor Yanukovych". These deputies, Poroshenko said, "clearly do not represent the people who elected them". Poroshenko also said that these Rada deputies were responsible for "the [January 2014] Dictatorship laws that took the lives of the Heavenly hundred". Poroshenko also stated that many of the (then) current MPs were "direct sponsors and accomplices or at least sympathizers of militant-separatists".
On 27 August 2014, the party congress of All-Ukrainian Party of Peace and Unity adopted a new name: "Petro Poroshenko Bloc" (BPP). In 2015, the Petro Poroshenko Bloc was renamed in "Petro Poroshenko Bloc "Solidarity"".
On 13 December 2014, Poroshenko stated that he did not want Ukraine to become a nuclear power again.
In June 2014, Poroshenko forbade any cooperation with Russia in the military sphere.
At the Parliamentary Assembly of the Council of Europe on 26 June 2014 Poroshenko stated that bilateral relations with Russia cannot be normalized unless Russia undoes its unilateral annexation of Crimea and returns its control of Crimea to Ukraine.
On Poroshenko's June 2014 Peace plan for Eastern Ukraine, Russian Foreign Minister Sergei Lavrov commented "it looks like an ultimatum".
On 26 August 2014, Poroshenko met with Russian President Vladimir Putin in Minsk where Putin called on Ukraine not to escalate its offensive. Poroshenko responded by demanding Russia halt its supplying of arms to separatist fighters. He said his country wanted a political compromise and promised the interests of Russian-speaking people in eastern Ukraine would be considered.
The European Union (EU) and Ukraine signed the economic part of the Ukraine–European Union Association Agreement on 27 June 2014. Poroshenko stated that the day was "Ukraine's most historic day since independence in 1991", describing it as a "symbol of faith and unbreakable will". He saw the signing as the start of preparations for Ukrainian EU Membership.
At his speech at the opening session of the new parliament on 27 November 2014, Poroshenko stated "we've decided to return to the course of NATO integration" because "the nonalignment status of Ukraine proclaimed in 2010 couldn't guarantee our security and territorial integrity". The Ukrainian parliament on 23 December 2014 voted 303 to 8 to repeal a 2010 bill that had made Ukraine a non-aligned state in a bill submitted by Poroshenko. On 29 December 2014 Poroshenko vowed to hold a referendum on joining NATO. On 22 September 2015 Poroshenko claimed that "Russia's aggressive actions" proved need for the enlargement of NATO and that the Ukrainian referendum on joining NATO would be held after "every condition for the Ukrainian compliance with NATO membership criteria" was met by "reforming our country".
Poroshenko set up an offshore company in the British Virgin Islands during the peak of the war in Donbass. Leaked documents from the Panama Papers show that Poroshenko registered the company, Prime Asset Partners Ltd, on 21 August 2014. Records in Cyprus show him as the firm's only shareholder. He said that he had done nothing wrong, and the legal firm, Avellum, overseeing the sale of Roshen, Poroshenko's confectionery company, said that "any allegations of tax evasion are groundless". The anti-corruption group Transparency International believes that the "creation of businesses while serving as president is a direct violation of the constitution".
Poroshenko has been married to Maryna since 1984. The couple have four children: Olexiy (born 1985), the twins Yevheniya and Oleksandra (born 2000) and Mykhailo (born 2001). Olexiy was a representative in the regional parliament of Vinnytsia Oblast. In November 2014, he became People's Deputy of Ukraine. Maryna Poroshenko is a cardiologist, who does not take part in public life, apart from her participation in the activities of the Petro Poroshenko Charity Foundation. Poroshenko became a grandfather on the day of his presidential inauguration of 7 June 2014.