Valladolid gave the recently-crowned champions a guard of honour before the match and then helped ensure the night would be a successful one for Tito Vilanova's men by conceding two sloppy first-half goals.
First a terrible pass from Jesus Rueda out of defence was intercepted by Xavi, who proceeded to put Pedro in for the opener, then Marc Valiente sliced a corner into his own net just before half-time to put Barca 2-0 up.
Barca were unable to build on that despite dominating the second half and were made to sweat a little at the end when Valladolid pulled a late goal back through Victor Perez's penalty - ruining Victor Valdes' hopes of a clean sheet on his 500th competitive appearance for the home side.
Valladolid never came close to an equaliser though as Barca moved onto 94 points with two games remaining.
The Catalan club's previous-best tally was the 99 they got in the 2009/10 season, while the only team to reach 100 points in La Liga history was Real Madrid last season.
Following the match, Barca were handed the Primera Division trophy for the fourth time in five years, having secured the title last weekend when nearest challengers Madrid could only draw at Espanyol.
Club captain Carles Puyol stepped aside when the moment came to lift the trophy, instead giving the honour to Vilanova and full-back Eric Abidal, both of whom have battled cancer in recent times.
Barca came into the match determined to reach the 100-point mark, but without the injured Lionel Messi they struggled to create much in the opening 20 minutes.
However, they were given a huge helping hand when Rueda handed Xavi possession 35 yards out as he tried to play the ball out from near his own box.
Xavi was not about to waste the unexpected gift, quickly progressing to the edge of the area before laying the ball off to Pedro on his right for his fellow Spain international to drill a low shot under Jaime.
That was one of the few shooting chances Barca had in the first half, but they still went into the break 2-0 up following another Valladolid defensive clanger.
Xavi's inswinging corner from the right was flicked on at the near post and Valiente, who was on Barca's book as a youngster, succeeded only in slicing the ball past Jaime as he tried to volley clear.
With the points seemingly in the bag, the only question looked to be how many more Barca might add in the second half.
They had the chances to record a big victory but found Jaime in fine form, the 32-year-old producing brilliant diving saves to deny Xavi, Martin Montoya and David Villa.
And when Jaime was beaten, Pedro's shot clipped the top of the bar while the same player also hit the side-netting with the goal at his mercy.
At the other end, Valdes, who became only the fourth player to make 500 appearances for Barca, was having a quiet night with his only save seeing him deny Oscar following good skill from the Valladolid forward.
Valdes did end up conceding in the 88th minute when Montoya was adjudged to have brought down Alberto Manucho in the area and Perez slammed the resulting penalty into the top corner.