Liverpool, who finished as runners-up in the Champions League last season, were forced to settle with a fourth placed finish in the league last season, which they secured during the final weekend of fixtures.
Pochettino's side ended talk of a Wembley hoodoo when they beat Jurgen Klopp's team 4-1 last October and he is not expecting a repeat of the disappointing performance at Vicarage Road.
Liverpool are without a league title since 1990 and a domestic trophy since 2012, and Neville said that their pursuit of breaking this duck could be burdened by European commitments.
"Gary should come over and tell me how that exactly works", Klopp told a press conference. I don't understand, do we play our kids or what?To focus on one competition can only be if you are out, or almost out, or if it's late in the season.
"Last year, for example, we had no chance to focus on one competition because we had to qualify for the Champions League and I don't think even Gary Neville would have said in the quarter-finals, "Come on, let [Manchester] City win".
The two sides meet in Saturday's early kick-off in what many people are tipping to be Liverpool's first serious test of the season. Bring your kids in the Champions League?
The £43.7million summer arrival has not featured in the matchday squad since being an unused substitute on the opening day of the campaign as he has been given time to adjust to Klopp's training methods.
"It's absolutely no problem". We don't play Champions League or what? I don't like the situation; it's not that I like to say to Fabinho, who is full of energy and desire and wants to be involved, "you are not involved this weekend".
"It is only the job to do sometimes because we have players that work together that much longer. Mauricio [Pochettino] has the same issues, we all have to work with what we've got".
"I don't know what he means with that, to be honest".