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The Brazil international spent four trophy-laden seasons in Catalonia, forming a formidable partnership alongside Messi and Luiz Suarez, before joining Paris Saint-Germain for a record €222 million in 2017 after his release clause was triggered.
Neymar has scored 50 times in 59 Ligue 1 outings since arriving at PSG and assisted a further 29 - only teammate Kylian Mbappe (99) has been directly involved in more goals in the competition in that time.
During his time with Barca, meanwhile, he was directly involved in 164 goals in 186 appearances, helping the club to eight trophies.
He left Barca under a cloud and has since been embroiled in a court battle with his former club over an alleged breach of contract and unpaid loyalty payments.
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The draws for the next round of the Champions League and Europa League produced some mouthwatering ties on Monday.
Chelsea and Liverpool were handed difficult clashes with Atletico Madrid and RB Leipzig respectively - while Manchester United, in the second-tier competition they last won in 2017, will meet high-flying Real Sociedad.
Sportsmail columnist CHRIS SUTTON has taken a look at all the ties that matter and given his verdict.
The draws for the next round of the Champions League and Europa League have been revealed
Bayern Munich had lifted the coveted trophy last season and will be aiming to retain it this year