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The acclaimed title, recognised as the fastest-selling Nintendo game ever released in the US, knocked last week's number one game LEGO Indiana Jones: The Original Adventures down to third place.
Super Smash Bros Brawl is now the third most successful UK Wii launch behind Wii Fit and Mario Kart Wii.
Elsewhere, EA's Xbox 360 and PS3 game Battlefield: Bad Company made its debut at number two, while the newly-released Wii exclusive Big Beach Sports entered the charts at number five.
Thanks to renewed stock levels of Nintendo's exercise game Wii Fit, the title saw sales rise by a staggering 643% as it climbed 23 places to this week's number four. In total, there are now four Wii-exclusive games in the all-formats top ten.
Beijing 2008, the multi-format official game of the Olympics, entered the top ten at number nine, while Rockstar's Grand Theft Auto IV almost fell out of the all-formats chart after sliding six places.
The top ten games in full:
1. (-) Super Smash Bros Brawl (Nintendo)
2. (-) Battlefield: Bad Company (EA)
3. (1) LEGO Indiana Jones: The Original Adventures (LucasArts)
4. (27) Wii Fit (Nintendo)
5. (-) Big Beach Sports (THQ)
6. (2) Metal Gear Solid 4: Guns Of The Patriots (Konami)
7. (11) Mario Kart Wii (Nintendo)
8. (12) Top Spin 3 (Take 2)
9. (-) Beijing 2008 (Sega)
10. (4) Grand Theft Auto IV (Take-Two)
Leisure software charts compiled by Chart Track, (C)2008 ELSPA Ltd
