The deal is subject to a medical.
The 34-year-old left Barca after 21 years, as they were unable to afford a new deal under La Liga's financial fair play rules.
Mauricio Pochettino's PSG finished second to Lille in Ligue 1 last season.
Considered in some quarters as the Greatest Of All Time (GOAT), Messi scored a record 672 goals in 778 games for Barca, the club he joined as a teenager, and has played for all his life (senior professional career).
The Argentine won the Ballon d'Or a record six times and lifted 35 trophies with the Catalan club.
With the imminent arrival of Messi, PSG would be bookmakers favourite to win the UEFA Champions League (UCL) trophy this season.
The club now has an enviable wealth of talent: Kylian Mbappé, Neymar Jr, Angel Di Maria, Sergio Ramos, Achraf Hakimi, Gianluigi Donnarumma, et al.
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