On 24 May 2013, Santos announced that they had received two offers for Neymar.[59] The following day, Neymar announced he would sign with FC Barcelona on 27 May 2013 and join the team after playing in the 2013 Confederations Cup. Neither Neymar nor the clubs released details on the transfer fee or personal terms, except to say he signed a five-year deal.[60] On 3 June 2013, Neymar was unveiled by Barcelona after passing medical tests and signing a contract that would keep him at the club through June 2018.[61] Neymar was presented at the Nou Camp in front of 56,500 fans a record turnout for a Brazilian player[62] Club vice president Josep Maria Bartomeu said Neymar's transfer fee was €57 million (£48.6m) (making him the 10th overall highest transfer) and his release clause was set at €190 million.[63] However, concerns remain that Neymar may be too lightweight for the transition to European football, and may need to bulk up in order to reach his peak physical condition
On 30 July 2013, Barcelona drew 2--2 against Lechia Gdańsk in a preseason friendly; this was Neymar's unofficial debut with the team, and he came on as a substitute.[65] On 7 August 2013, Neymar scored his first goal in a Barcelona shirt during a 7--1 friendly win over the Thailand national team in Bangkok.[66]
Neymar made his competitive debut for Barcelona during the opening game of the 2013--14 La Liga season as a 63rd minute substitute in a 7--0 win against Levante UD.[67] On 21 August, he scored his first competitive goal for the club in the first leg of the 2013 Supercopa de España against Atlético Madrid.[68] On 18 September, he made his UEFA Champions League debut, assisting a Gerard Piqué goal as Barça beat AFC Ajax 4--0 in their opening match of the 2013--14 tournament.[69] On 24 September, Neymar scored his first goal in La Liga in Barça's 4--1 defeat of Real Sociedad at Camp Nou.[70]
On 26 October 2013, Neymar scored the opening goal in his first El Clásico appearance as Barça beat Real Madrid 2--1 at Camp Nou. [71] Later in the match he assisted the team's winning goal scored by Alexis Sánchez.[72]
On 11 December 2013, Neymar recorded his first Champions League goals as he scored a hat-trick in a 6--1 win over Celtic in Barça's final Group H match.[73]