The lapse was all Murray needed as he snatched the third set before the weather gods intervened to force the two tennis titans to endure a restless night's sleep.
The chance to join Roger Federer, Rafael Nadal, Andre Agassi and Rod Laver as only the fifth man in the 47-year era to win all four majors in Melbourne, Paris, London and New York appeared to unsettle Djokovic as the Serb's jitters resurfaced on Saturday.
The world No.1 dropped serve with a flurry of unforced errors to concede the fourth set as Murray threatened to pull off a famous win.
Alas, the third seed's hopes of becoming the first Brit to make the men's final in Paris since Bunny Austin in 1937 floundered as he handed Djokovic a service break and a 3-0 lead in the deciding set.
There was to be no second comeback as the five-times Australian Open champion grabbed a double break in the sixth game before serving out the epic encounter after four hours and nine minutes.
Djokovic's stirring win confirmed his title favouritism after suffering years of heartache in the French capital at the hands of claycourt colossus Rafael Nadal.
Djokovic not only lost the 2012 and 2014 finals to the undisputed king of clay, but also semis against Nadal in 2007, 2008 and 2013 and a quarter-final in 2006, the first of the grand slam giants' record 44 professional encounters.
This time, though, Nadal won't be standing in Djokovic's way in the title match after the world No.1 ended the Spaniard's near-decade-long rule of Roland Garros in a quarter-final demolition job on Monday.
Djokovic leads Wawrinka 17-3 in head-to-head meetings, although the pair's past four grand slam encounters have ended in five-set classics.
Wawrinka ousted Djokovic en route to his first grand slam triumph at last year's Australian Open before succumbing to the world No.1 in a semi-final return bout in Melbourne in January.
Djokovic and Wawrinka both must smash longstanding Roland Garros hoodoos to lift the trophy on Sunday.
Djokovic is striving to become the first man since Jim Courier in 1992 to complete the Australian and French Open double in the same season.
Wawrinka, who shattered French hopes for another year with a tense 6-3 6-7 (1-7) 7-6 (7-3) 6-4 semi-final victory over 14th seed Jo-Wilfried Tsonga, can become the first former junior champion since Mats Wilander in 1982 to also win the men's crown at Roland Garros.
-AAP