Barcelona moved to within a whisker of a second straight La Liga crown when Lionel Messi, Bojan Krkic and Pedro earned a nervy 3-2 win at 10-man Sevilla on Saturday.
Real Madrid kept the gap to one point with one match left when a late flurry of goals gave them a 5-1 victory at home to Athletic Bilbao, who also had a player sent off, but Barca now only need a win at home to lowly Real Valladolid next weekend to make sure of the title.
Barca beat arch rivals Real in both this season's "Clasicos" and have lost only once all season, scoring 94 goals and conceding 24.
They extended their record points tally to 96 from 37 matches with Real in second on 95 and Valencia, who lost 2-0 at Villarreal but are already assured of a Champions League spot in third, trailing on 68.
Sevilla are fourth on 60 and Real Mallorca fifth on 59 after their 1-0 defeat at Deportivo Coruna.
Real's final match is at Malaga, who are one place below Valladolid after a 2-1 reverse at sixth-placed Getafe and also fighting to avoid the drop.
"We are not going to lose hope," Real defender Sergio Ramos, who netted his side's third goal, told reporters.
"We have to carry on doing our jobs and if Barca win the league with 99 points they'll have to be congratulated."
Barca had already surpassed the previous La Liga record of 92 accumulated by Real under Fabio Capello in the 1996-97 season when there were 22 teams rather than 20.
La Liga top scorer Messi put them in front in the fifth minute at the Sanchez Pizjuan when he controlled Maxwell's pass on his chest and drilled a low shot past goalkeeper Andres Palop for his 32nd of the season.
A sublime first-time pass from midfielder Xavi sent teenager Bojan clear to score a second for the visitors in the 28th and Barca looked to be cruising when Pedro added a third with a snap shot from the edge of the area in the 62nd.
Two Sevilla goals inside three second-half minutes from Frederic Kanoute and Luis Fabiano set Barca's nerves jangling, coach Pep Guardiola at one point smashing the side of the dugout three times with his elbow in frustration.
The final whistle prompted wild celebrations from the Barca players and their knot of travelling fans high in the stands.
"You can never write off Sevilla and we suffered at times," goalkeeper Victor Valdes told reporters. "We have to keep in mind now that Valladolid will be a tough opponent."
At the Bernabeu, a Gonzalo Higuain shot struck the hand of Fernando Amorebieta in the penalty area in the 20th minute and the referee showed the Bilbao defender a straight red card.
Ronaldo sent goalkeeper Gorka Iraizoz the wrong way with the spot kick but Real were stunned four minutes before the break when midfielder Fran Yeste burst clear and finished with aplomb past Iker Casillas.
With the score at 1-1 and Barca winning in Sevilla, Real's title hopes were slipping away but Higuain, Sergio Ramos substitute Karim Benzema and Marcelo struck four goals in the last 20 minutes to keep Real hot on Barca's heels.
"It's a difficult situation but Valladolid are battling for survival and in football anything is possible," Real coach Manuel Pellegrini told a news conference.
"Our duty is to make sure that if Barca are champions they will have to do it with 99 points."
Three points separate five teams battling to avoid the drop ahead of the final matchday.
Valladolid, Malaga, Tenerife and Racing Santander all have 36 and Xerez are hanging on by a thread on 33 after their 3-2 win at home to Real Zaragoza.