The great moment for Raul came 15 minutes into Sunday's away game against lively but naive Sporting Gijon, dpa reported.
Spain defender Sergio Ramos tried a speculative cross-shot from the right.
Raul, like all great goalscorers, was in the right place at the right time, close to the penalty spot as the cross came over.
He stuck out his trusty left foot and poked the ball past Gijon goalkeeper Inaki Lafuente to make it 1-0 - and to break the record of Alfredo Di Stefano.
13 minutes from the end of the game, Raul scored his 309th league goal, turning in the rebound after Lafuente had spilled a shot from Gonzalo Higuain.
The great Di Stefano scored 307 Liga goals for Real, between 1953 and 1964 - at the same time as helping Real to winning six European Champions Cups.
Now Raul - who has helped Real to three Champions League titles - has broken the Argentine master's goals record by scoring 309.
Raul has been playing for Real longer than Di Stefano did - he made his debut in 1994 - but that should not detract from the magnitude of his achievement.
"This is a good day for me," said the 31 year-old veteran after the 4-0 romp in Gijon.
As usual, though, Raul was quick to put the achievements of the team before his own personal ones, adding that "but what is really important is not the record, but that the team continues to win."
Typical Raul, the consummate one-club team-man, an anomaly in an age when top football stars, encouraged by their avaricious agents, are usually keen to make big-money switches from one top club to another.
He claims that he has never been interested in leaving the Estadio Bernabeu, though there has been no shortage of offers for him.
Raul told the Spanish media last year that one of the secrets of his success has been a calm, gratifying personal life.
He married famous model Mamen Sanz in 2000, and has four sons with her. His hobbies are reading, hunting and bull-fighting.
Two years ago he raised eyebrows by admitting that he slept in an oxygen tent, in order to improve his physical resistance and muscular prowess - and to keep his career on fire after so many years at the top.
It has often been said that Raul has no special qualities that make him stand out as a player: he is not especially fast, good in the air or in the dribble - and he does not possess a particularly fierce shot.
However, he is the classical "Sniffer", almost always in the right place at the right time, to stab home a loose ball that has been bouncing around the penalty area.
Few of his goals are memorably aesthetic, but they have all been important, especially the ones he scored in the 2000 and 2002 Champions Cup finals.
Ironically, he comes from a family of Atletico Madrid supporters, and played in the youth sections of that club until being poached by Real in 1991, aged 14.
Argentine coach Jorge Valdano raised eyebrows by picking Raul, then a scrawny unknown 17 year-old, to make his debut away to Zaragoza in October 2004. He missed several good chances that day, but scored his first goal a week later in the derby against Atletico - and has not stopped scoring since then.
He helped Real to the Liga title in 1995 and 1997, and made his Spain debut in 1996. He made a total of 102 appearances for Spain, scoring 44 goals in the process, and led the attack for his country at the 1998, 2002 and 2006 World Cup finals.
Controversially, Luis Aragones declined to pick him again for Spain after 2006, though he was vindicated in his decision by guiding "La Seleccion" to the 2008 European Championship, with David Villa and Fernando Torres in attack instead of Raul.
When dropped by Spain, Raul was written off as finished by many commentators. However, the goals have not stopped - as Gijon found out to their cost on Sunday - and his influence as club captain has still not waned.
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