Tottenham will enter the match off the back of a 2-1 defeat at Watford before the international break, while Liverpool beat Leicester City to make it four wins from four at the start of the new campaign.
Merson has backed Liverpool to emerge victorious from the clash at Wembley, but has said that the Reds will find it "so difficult" to beat Manchester City to the Premier League title.
"I fancy Liverpool based on the counter-attack game. This game is bigger for Tottenham than it is for Liverpool - this is a game Spurs can't afford to lose, they've got to have a go especially after what happened at Watford. Liverpool will pick them off," Merson told Sky Sports News.
"If you want to win Premier League titles then you have to win these games, so Liverpool will be judged on this too. I think they'll win this one but toppling Manchester City for the title will be so difficult."
Tottenham recorded a 4-1 win in the corresponding Premier League match last season.