Rafael Nadal failed to reach the final of the Monte Carlo Masters for the first time since he was 16 as he was defeated in straight sets by fellow Spaniard David Ferrer.
Maria Sharapova is unbeaten at the indoor tournament having won both the 2012 and 2013 crowns on her two previous appearances.
Roger Federer beat holder Djokovic 7-5, 6-2 to reach the final.
Sixth-seeded David Ferrer looked in good form when he beat eight-time champion Rafael Nadal in Friday's quarterfinals, but was unable to withstand Stanislas Wawrinka's aggressive approach, and spent much of the match pinned behind the baseline.
The third-ranked Agnieszka Radwanska hit 33 winners to Silvia Soler-Espinosa's 17 to claim the match on the outdoor red clay court at the Estadio Olimpico in Barcelona.
Andrea Petkovic opened with a 6-1, 7-6 (7) win over Sam Stosur while top-ranked German player Kerber had little difficulty beating Casey Dellacqua 6-1, 6-0 in 51 minutes on outdoor hard courts at Pat Rafter Arena.
Serbian World No.2 Novak Djokovic will face off in a Saturday semi-final against Roger Federer, whom he beat in last month's Indian Wells final but lost to in Dubai in February.
Spaniard David Ferrer, 32, who reached a career-high world number three ranking last year, outlasted his World No.1 rival and good friend Rafael Nadal in a marathon 75-minute first set to seize the advantage.
Stanislas Wawrinka finished with 30 winners and 28 unforced errors and never faced a break point.
Rafael Nadal is forced to serve with just one tennis ball as the other has been repeatedly popping out of his pockets. Nadal says it is proving to be a hindrance in the ongoing Monte Carlo Masters.
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