Chakvetadze played well in the first set, responding to Williams' power-hitting with crafty counter-punching and big hitting of her own, but the Russian couldn't maintain her form in the second set.
"She's able to chase down a lot of balls,'' Williams said. "Against a player like that, it's just important to focus on what's happening on my side of the net and realize that I might have to hit two or three extra (balls). The reply might be a little shorter so I might have the chance to come in to be more aggressive.''
Williams also beat the top-ranked Jelena Jankovic of Serbia in straight sets on Thursday in the semifinals against Team Europe at the warm-up event for the Australian Open.
Chakvetadze was up 4-2 in the first set, but Williams broke back in the eighth game. The Russian then missed two straight forehands in the tiebreaker to give Williams a 6-0 lead.
"It's tough to play her,'' Chakvetadze said. "She hits very hard.''
Williams broke Chakvetadze twice to take a 5-1 lead in the second set, but the Russian saved two match points to hold serve in the seventh game and then broke Williams to stay in the match. However, Williams broke right back, sealing the win as Chakvetadze missed a forehand down the line.
Argentina's Gisela Dulko will play Russia's Vera Zvonareva later Friday.
Williams will play Zvonareva and Dulko faces Chakvetadze on Saturday, before a final doubles match.
Guardiola Pleased Yet Sad With Barcelona Defeat
Russia level with Team Americas at HK exhibition
