Liverpool signed the 25-year-old Brazil global from Roma last month, smashing the world record for a goalkeeper in a deal worth £67m.
Napoli are yet to face a non-Italian side this pre-season beating Gozzano, Carpi and Chievo comfortably and Liverpool will be their first real test as they approach more challenging fixtures against Borussia Dortmund and Wolfsburg.
"It's pretty likely [he will play against Napoli]", Klopp told Liverpool's official website.
Liverpool will have to make do without the services of Marko Grujic, Danny Ings, Adam Lallana and Joel Matip for their penultimate pre-season clash against Napoli on Saturday, the club confirmed.
A video released on LFCTV GO providing an inside look at a high intensity training ground showed Liverpool players reacting to a superb save the goalkeeper made.
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The right-back returned to Reds training earlier this week after representing England at the World Cup this summer.
"I think goalkeepers are important to any team".
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Klopp who is now with the squad in France said all their summer signings, Alisson Becker, Fabinho, Naby Keita and Xherdan Shaqiri will get to know their new surroundings before their league opener against West Ham United five days later.
He said: "Although these two weeks don't seem like a long time, it's enough for us to be ready for our first game against West Ham".
"This initial training session has been useful for me to see what our playing style should be in the Premier League".