The Argentine scored twice as the Blaugrana thrashed Rayo Vallecano 6-0 on Saturday to go back to the top of the league.
The Blaugrana talisman opened his account with a delicate chip over Ruben and later finished emphatically from Alexis Sanchez's pass before being substituted in the 74th minute.
Messi's spate of goals since the turn of February elevated him to fifth in La Liga's all-time scoring charts with 226 goals, sitting only one strike behind Madrid great Alfredo Di Stefano before Saturday's fixture.
His latest brace takes his Barcelona tally to 228 goals in just 263 appearances and allows him to surpass his compatriot and move into joint-third place beside Raul on 228 goals.
The 26-year-old is also La Liga's second all-time top foreign goalscorer, with Mexican Hugo Sanchez holding that record on 234.
Athletic Bilbao icon Telmo Zarra, who starred for the Basques between 1940 and 1955, tops the charts with 251 goals.