Messi struck in the 36th and 68th minutes of a completely one-sided match at the Nou Camp to move above Alfredo Di Stefano (227) in the record books and level with another Real Madrid legend, Raul, on 228 La Liga goals.
Adriano opened the floodgates in just the second minute and Alexis Sanchez (53), Pedro Rodriguez (56) and a fantastic Neymar goal (89) added to Messi's double.
There were ugly scenes, though, at El Madrigal where Celta Vigo's unlikely 2-0 win over Villarreal was marred by a serious incident which almost saw the match abandoned.
Fabian Orellana had just headed Celta into the lead late in the second half when what appeared to be a smoke bomb was thrown on to the pitch, forcing the referee to take the players from the field and leading to most of the supporters leaving the stadium.
It led to a lengthy stoppage - and considerable confusion as at one stage it seemed the match would not continue - but eventually the players re-emerged and the four remaining minutes were played, enough time for Nolito to add a barely deserved second goal for the visitors.
Atletico Madrid reaffirmed their title aspirations with a commanding 3-0 win at home to Real Valladolid, ending a three-game losing streak.
Two goals in the opening four minutes from Raul Garcia and Diego Costa got Atletico off to a flying start and Diego Godin added a third in the second half to seal a morale-boosting victory for Diego Simeone's men.
The win briefly put Atleti top, until Barca overtook them again on goal difference with their victory.
In the day's other game, David Barral's excellent volley was all Levante needed to see off Almeria 1-0.