Nikolay Davydenko's reign at the Kremlin Cup was brought to an end on Friday with defeat to Marat Safin in the quarter-finals.
Seventh seed Safin made the most of his powerful serve to beat the top seed 7-6 (7-5) 4-6 6-4 in Moscow.
A former world number one and two-time grand slam champion, Safin fired 17 aces to outlast the two-time defending champion, denying him a fourth shot at the title.
Safin also put an end to his own winless streak to Davydenko, having lost his last four matches against his Russian compatriot.
Safin broke Davydenko in the fifth game of the decisive set and held on from there, winning in two hours 28 minutes.
Safin will now face Mischa Zverev in the last four after the unseeded German posted a stunning 6-4 3-6 7-5 victory over Viktor Troicki.
Zverev trailed 5-1 in the final set and faced two match points, but he saved both and broke for a 5-2 deficit.
Zverev then broke Troicki twice more to complete the stirring comeback.
It is the first ATP semi-final appearance for Zverev, who had lost in his three previous quarter-finals this year.
In another quarter-final, Fabrice Santoro prevailed in all-French match-up when fourth seed Paul-Henri Mathieu retired due to illness with Santoro leading 6-3 2-0.
Santoro, who was a semi-finalist in Moscow two years ago, will face Russian Igor Kunitsyn in the last four.
Kunitsyn dominated Jeremy Chardy of France 6-4 6-2 in 63 minutes to move into the Moscow semis for the third time in four years.
In the women's draw, Jelena Jankovic battled into the last four at the expense of Flavia Pennetta.
The top-seeded Serbian was a 7-6 (8-6) 6-3 winner over the unseeded Italian.
The victory extended Jankovic's winning streak to 10 matches and set up a semi-final clash with defending champion Elena Dementieva, who needed three sets to oust Russian compatriot Nadia Petrova 6-4 4-6 7-6 (8-6).
Jankovic, who overtook Serena Williams for the world number one ranking at the start of the week, is seeking her third title in as many events.
The first player on the WTA Tour this season to reach the 60-win mark, Jankovic needed nearly two hours to dispatch Pennetta one day after enduring a two-and-a-half-hour marathon victory over Vera Dushevina.
Pennetta, who upset Venus Williams in the opening round and has won two titles this season, held early leads in both sets but eventually succumbed.
A Russian player has won in Moscow in four of the last five years, and the third-seeded Dementieva will be hoping to continue that trend with a second successive title.
Dementieva struggled with her serve against Petrova though en route to reaching the semi-finals for the 10th time in 17 events this year.
Despite committing eight double-faults, Dementieva saved seven of 12 break-point chances to prevail in two hours and 44 minutes.
The 26-year-old Petrova, who had reached the semi-finals or better in four of her last five events - including a title in Cincinnati - committed 72 unforced errors.
Second-seeded Russian Dinara Safina booked her spot in the last four with a 6-4 7-5 victory over fifth-seeded countrywoman Svetlana Kuznetsova.
Safina, who has lost just six of her last 50 matches, will be looking to reach her eighth final of the season when she takes on Vera Zvonareva in the semis.
The seventh-seeded Zvonareva advanced by defeating Slovakia's Dominika Cibulkova 7-5 6-4.
The 22-year-old Safina has won four titles