Valdivia was born in Maracay, Venezuela, to Chilean parents Luis Valdivia and Elizabeth Toro. His father worked as a corresponsal at LAN airlines since 1974, reason which Jorge was born there in 1983. In 1985, Valdivia family returned his homeland and moved to capital city Santiago. There they settled in the commune of La Florida. Noteworthy, he was interested on baseball during his few years at Venezuela, and once in Chile, Valdivia began to develop a taste for football.

In 1993, Valdivia joined Colo-Colo’s football academy. He was promoted to first team in 2003, at the age of nineteen. Nevertheless, he was demotivated by his teammates, like captain Marcelo Espina, complemented by the misbehavior outside the field.

After falling out of Colo-Colo’s first team figures, Valdivia was loaned to fellow Chilean Primera División side Universidad de Concepción. He made his professional debut for Concepción on 16 March 2003, coming on as a second-half substitute for Pablo Abdala in a 2–1 Primera División away loss against Cobresal. During his first start on 6 April, he scored his team’s last in a 3–1 home win against Unión Española.

Born in Venezuela, Valdivia was eligible to play for the national team of either country. However, he appeared with Chile’s U20 in the 2003 South American Youth Championship, only making two appearances in a tournament which Chile finished last in the group stage.

Valdivia also represented his country in the 2004 Pre-Olympic Tournament — alongside players like Claudio Bravo, Jean Beausejour, Luis Pedro Figueroa or Mark González — where he had an impressive performance. In June of that year, he earned his first senior cap for Chilean national team against Mexico. Also that year he became part of the 2006 FIFA World Cup qualifying nominees under Juvenal Olmos as head coach, who choose him to play the Pre-Olympic. Nevertheless, Chile failed to qualify the World Cup.

Then, in 2006, Valdivia helped his club to achieve the Torneo Apertura, where once again he reached an impressive performance, which was polished by the coach in the age, Claudio Borghi. Noteworthy, he highlighted in a team which had players like Chilean internationals Claudio Bravo, Matías Fernández and Humberto Suazo.

On 5 August 2006, Valdivia completed his move to Brazilian club Palmeiras for a US$3.5 million transfer fee. His signing was the club’s most expensive transfer – in the age – for a foreign player. After an unsuccessful season, he had a revitalizing 2007 where he reached four honours for his performances: Campeonato Paulista Most Valuable Player, Prêmio Craque do Brasileirão, Bola de Ouro and Troféu Mesa Redonda, that put him as the season’s best playmaker of Brazilian football. His further consecration at the Verdão was the obtention of 2008 Campeonato Paulista title, where for his performances he came to cost US$40 dollars.

Valdivia scored his first international goal for Chile in an exhibition match against Paraguay in Vina del Mar on 16 November 2006 during a 3–2 victory.

In June 2007, Valdivia was chosen in Chile’s Copa América squad, which they were eliminated in quarterfinals after a 6–1 thrash of Brazil. However, before the game against Brazil, he alongside five players went on a spree and once leaked the press they received a 20-game ban from the federation (ANFP). Then Nelson Acosta resigned as national team coach.

In August 2008, it was reported that Valdivia joined United Arab Emirates’ Al Ain in an €8 million deal for a two-year contract. At the Emirati club, he won the Etisalat Emirates Cup, President Cup and the Super Cup. There, he became a top idol in the history of the club, so much so that Mohamed bin Zayed Al Nahyan, president of the club, offered him a lifetime contract (which Valdivia didn’t sign).

A year and half later, he was re-considered by Marcelo Bielsa after calling-up him to a friendly game with Turkey on 5 August 2008. One month later, on 7 September, Valdivia made his debut for the 2010 World Cup qualifying in a 3–0 loss with Brazil, which he was sent off for double-yellow card. On 10 October 2009, he scored the last goal of the 4–2 win over Colombia at Medellín that finished Chile’s 12-year World Cup absence since 1998.

In January 2011, Bielsa left abruptly stepped down as coach following differences with the federation, but Valdivia continued being considered in La Roja by Claudio Borghi, his former coach when he played in Colo-Colo. In June, he was included in the 23-man list to face the Copa América. He made three starts of Chile’s four games in the competition, which they were eliminated in quarterfinals by Venezuela (where Valdivia had a crossbar), rival which only one-time Chile lost in its history. However, Valdivia was included in the team of the tournament. Months later in December 2011 before a 2014 World Cup qualifying game with Uruguay in Montevideo, he was involved in another scandal alongside Jean Beausejour, Gonzalo Jara, Arturo Vidal and Carlos Carmona after arriving 45 minutes later and intoxicated to the team’s concentration at Juan Pinto Durán. They subsequently received a 10-game ban and Valdivia once finished the punishment it wasn’t be considered by Borghi during the qualifiers and friendlies.

On 8 March 2013, after 16 months of the incident, Valdivia was re-called by Jorge Sampaoli, including him in the call-up for the qualifying games against Peru and Uruguay. His official re-debut was on 7 September against Venezuela in a 3–0 victory at Estadio Nacional. On 15 October, following a 2–1 win over Ecuador, Chile reached its eight qualification to a World Cup and its first consecutively.

On 1 June 2014, Valdivia was selected in Chile squad for the 2014 FIFA World Cup in Brazil. On 13 June, Valdivia scored his first World Cup goal during Chile’s opening group match against Australia, netting the team’s second goal in a 3–1 victory. The following two group games he came as substitute against Spain and the Netherlands, being an unused substitute in the round of 16 game against Brazil, which eliminated Chile on the penalties after 1–1 at Estádio Mineirão. The last fact motivated Valdivia to announce his international retirement, communicated via Twitter on 17 July 2014. However, in November he backtracked his decision later on, and was called for friendly matches against Venezuela and Uruguay, selling his re-debut with a goal and a brilliant performance in 5–0 win over the Venezuelans at Talcahuano.

On 25 June 2015, it was reported that Valdivia would return to United Arab Emirates to sign for Al-Wahda, after rejecting an offer from China’s Guangzhou Evergrande. The player and the club reached a two-season contract and a US$2.8 million salary per year.

On 19 June 2017, Valdivia returned to his first club Colo-Colo. In December 2019, Colo-Colo announced they would be not renewing his contract.

On January 16, 2020 Valdivia signed with Liga MX side Morelia.