Two goals in the final 12 minutes of a pulsating clash set up Belgium for a World Cup second-round showdown with new tournament favourites Brazil.
Striker Wesley Sonck and captain Marc Wilmots, capping a superb man-of-the-match performance, fired home the goals to end Belgium's miserable run of seven World Cup matches without a victory.
With co-hosts Japan topping Group H following their fine win over Tunisia in Osaka, Belgium just managed to hang on to the runners-up spot.
At one stage Russia were within sight of a date with the brilliant Brazilians in Kobe on Monday.
Needing a draw to guarantee their place in the last 16, they started the match in disastrous fashion, albeit conceding one of the goals of the tournament to date.
Andrei Solomatin's shirt tug on Wilmots led to Walem scoring only his second goal in 36 appearances, sweeping a 24-yard left-foot free-kick over the Russian wall and into the left-hand corner of keeper Ruslan Nigmatullin's net.
Glen de Boeck and Gert Verheyen missed glorious chances to double Belgium's lead just before the break, seven minutes after which Vladimir Bestchastnykh hauled Russia level.
Dmitry Khokhlov's through ball picked out advancing Dmitri Sychev, the 18-year-old hailed as the hottest property in Russian football, only for his goal-bound flick to be superbly blocked at point-blank range by Geert de Vlieger.
The ball spun off the keeper's body for Bestchastnykh to sidefoot home from eight yards.
It was now Belgium in need of the qualifying goal, and they continued to look the more dangerous side, and indeed should have regained the lead when Walem stabbed a six-yard shot into the sidenetting.
Belgium were not to be denied and within eight minutes of coming on as a sub for Mpenza, Anderlecht star Sonck headed home a Walem corner from just six yards.
The insurance goal followed four minutes later from Wilmots as he turned inside the challenge of Yuri Kovtun after receiving a through ball from Bart Goor before firing a crisp, 18-yard right-foot shot beyond Nigmatullin.
Sychev pulled one back as he slipped a close-range shot past the advancing de Vlieger, but it was all in vain.
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