Valverde's side are 3-0 up ahead of Tuesday's return at Anfield after Lionel Messi put the Reds to the sword at Camp Nou last week, but last year Barca crashed out despite holding a three-goal advantage.
Leading 4-1 against Roma, Barca contrived to lose 3-0 at the Stadio Olimpico, exiting the Champions League at the quarter-final stage via the away goals rule.
Messi subsequently made it clear Champions League success was Barca's priority this season and Valverde wants Barca to right the wrongs of that Roma defeat.
"It's an experience to learn from, but the good thing about football is you always get another chance," Valverde told reporters when asked about the Roma game.
"Nothing in football is written, you have to go out there and do it. PSG [in the last 16 in 2017] - people said if they scored it was over but we went out there and scored six.
"Looking at this full press conference and all the tickets that have been sold, I don't think there is any danger of that [complacency] happening. But Liverpool are a good team, so who knows what could happen.
"Let's wait and see what happens tomorrow, Jurgen Klopp will still think he can win the double of Champions League and Premier League."
Liverpool are not only 3-0 down, but without strike duo Roberto Firmino and Mohamed Salah due to injury.
Valverde, though, insists he will be taking nothing for granted despite his side's strong position in the tie.
"We need to ignore the first leg, it would be an error to think that would help us," Valverde added. "We're playing at Anfield in front of a very difficult crowd because of the passion and the atmosphere they generate.
"It would be a mistake to think we just need to control the game. Control is no use unless you can also attack and this is why sometimes we have to change our style.
"There are different players in the team now and perhaps teams have got wise to the way we play. So sometimes instead of just passing the ball we have to get the ball forward quicker.
"We've played at big stadiums like San Siro and Old Trafford and done well this season, I think we can cope with the pressure."
"Your most important game is always the next one," Valverde added. "The Champions League is always important but if you ask me if this is my most important game at Barcelona, then maybe it is."