He said: "It was a memorable day for me and I would love a repeat of that scoreline but I can't see it to be honest!
"It would be nice to get any sort of positive result but you've got to give a lot of respect to players plying their trade at the top level - it's where every professional footballer wants to play.
"They've got a lot of international players and I'm really excited to be coming up against them again."
Pools claimed an impressive 2-0 win against Premier League side Stoke at Victoria Park in the last round, while West Brom were put to the sword by the League One outfit in the Carling Cup at the end of August.
Humphreys admits the giantkilling double has given his team-mates extra confidence as they look to pull off another shock but he suspects West Ham will be a different proposition.
"Stoke was a very tough test," Humphreys said.
"They were a very strong side and were dangerous from set-plays but I felt we coped with that really well on the day.
"West Ham will pass the ball a lot more.
"I've seen them play twice in the last couple of weeks and they've been impressive. They have very much a footballing manager in Gianfranco Zola, so it will be a different test for us.
"I've been involved in some big games since I've been at Hartlepool but this is definitely up there with the play-off final in Cardiff [when Hartlepool lost in extra-time to Sheffield Wednesday].
"I can't wait for the game. West Ham have such a great history and are a really successful club so it's a great occasion for us.
"We have to go into the game with the belief we can get through the tie or we'll have lost before we've started."
Humphreys, who was named Hartlepool's Player of the Century at the end of last season, admits to having mixed emotions over West Ham's sale of Craig Bellamy to Manchester City, because he knows Zola has plenty of other attacking options at his disposal.
"They will certainly miss Craig as he's a great player but they'll just bring somebody else in who is equally as good!" he added.
"(David) Di Michele came into the team and scored against Fulham, so we're under no illusions as to the Premier League and international quality we will be up against."