Munir made his UEFA Youth League debut with the Juvenil side against Ajax U19, where he scored two goals. He scored braces against Milan U19 and Copenhagen U19, finishing the tournament scoring 11 goals in 10 matches. He scored a brace in the final against Benfica U19. On 3 March 2014, he extended his Barça contract until June 2017.
After being an unused substitute against Tenerife and Deportivo de La Coruña, Munir made his professional debut for Barcelona B on 2 March 2014 in a 1–2 away win against Mallorca in the second division, coming as a 72nd-minute substitute for Sandro. He scored his first goal as a senior player in a 2–1 home win against Girona on 19 April.
On 24 August 2014, Munir made his official debut for the first team in La Liga, against Elche at Camp Nou. He started the match and scored the second goal of an eventual 3–0 win before being substituted after 67 minutes for Pedro. Eight days short of his 19th birthday, he became Barcelona's third-youngest goalscorer after Bojan and Lionel Messi. Munir was a nominee for the 2014 Golden Boy Award.
On 29 August 2014, Munir was called up for the first time as one of 21 players for Albert Celades' Spain under-21 team to face Hungary and Austria in September. However, after an injury to Diego Costa, Vicente del Bosque called Munir up to the senior squad for the first time ahead of a UEFA Euro 2016 qualifier against Macedonia on 8 September. He made his debut in that match, replacing Koke for the final 13 minutes of a 5–1 victory at the Estadi Ciutat de València. He said after the match he never considered playing for Morocco.