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Supporters are clamouring for the young duo's inclusion after vibrant seasons in the Premier League, and Roy Hodgson has been urged to select a bold and attacking formation against the patient Italians.
Sterling, 19, excelled for Liverpool on the wing yet was also adroit in a central forward role. He attained his second full cap in the friendly win against Peru in May but was sent off in last week's 2-2 draw with Ecuador in Miami, and subsequently missed the Honduras stalemate through suspension.
Barnes reckons the teenager should be eased into the World Cup finals.
"I wouldn't start him," Barnes told Huffington Post UK. "If you look at the game against Honduras, I think that's very close to the team [Hodgson] will play. First of all, Roy Hodgson has to be true to his own ideologies and his own philosophies. We've known him for 20 years, we know the team he plays, we know how he likes to play, so going with all these attacking players, it doesn't mean Roy Hodgson should do that, because that's not who he is.
"Secondly, I wouldn't want to put so much pressure on Sterling or Barkley at the start of the World Cup, because they've been playing club football for one year in the first team - only one year - and now they're in the international team, which is OK, but to put pressure on them to go to the World Cup? No matter what people say they will be under pressure.
"We've had it already with Barkley in the newspapers, and people say 'Barkley should play because he's going to do well' and if he doesn't do well that could stifle his development and Sterling's. I would use both of them as impact players."
England should learn from Theo Walcott's World Cup call-up in 2006, according to Barnes. Seventeen at the time, Walcott had not played since his transfer to Arsenal in January that year, as Sven-Göran Eriksson "gambled" on an unknown quantity he did not even bother playing in the Germany finals.
Walcott, overlooked for the 2010 tournament and injured this year, has struggled at international level, scoring just five goals in 36 caps. Barnes is concerned a similar fate could befall Sterline or Barkley, despite their seniority at club level.
"I'm looking forward to this team with Barkley and Sterling in the next two years and the  World Cup, but we could stifle their development if we put them in too soon and things don't go well," Barnes added. "We saw when Walcott went to the World Cup at 17 and it took him a few years because of the pressure that was on him. So why put that pressure on them when we're not going to win the World Cup?"
Sterling, like Barnes, was born in Kingston, Jamaica, which has drawn lazy comparisons between the duo, enhanced by their Liverpool allegiances. Barnes experienced his own World Cup disappointment when Bobby Robson overlooked him during the 1986 finals in Mexico until the quarter-final against Argentina.
With England trailing 2-0, the then-22-year-old replaced Trevor Steven for the final 14 minutes and crossed for Gary Lineker's goal and almost claimed a second assist. However he insists it is inaccurate to suggest Sterling is in a similar situation.
"It was only when I came on for the last 14 minutes that people said afterwards 'Oh, he should've been starting,'" Barnes recalled. "In 1986 I had already been an international for three years, I'd been playing at the highest level for five years. Raheem Sterling has played one year, I was older and much more experienced.
"The issue I have with the young players isn't the ability, they have great ability, it's the experience they have and the consistency that only comes with playing over a period of time. To make a comparison between Raheem Sterling and me in 1986 doesn't hold up. It's the same with Gazza and Ross Barkley. In 1990 Paul Gascoigne had already been playing top quality football in the First Division at the time for four years, so it's different. We have to allow them to develop so they can develop consistency, because it could go badly wrong.
"In 1986, of course, I believe I should have started, but I had made my debut in 1983. I had already been playing first-team football for five years. The comparisons with me and someone playing first-team football with three caps over a year is not accurate."
Barnes' preference is for Hodgson to retain Danny Welbeck against the Italians, a match he describes as "a mustn't-lose game, rather than a must-win". He believes England will reach the quarter-finals, but is adamant they are "not going to outplay teams", citing the gung-ho recklessness that was punished by the Ecuadorians.
Despite Wayne Rooney's struggles in the three warm-up matches, Barnes is adamant the forward remains England's "most important player", along with captain Steven Gerrard.
"He plays for the team, he understands international football," Barnes said. "It's not about playing well, scoring goals and outplaying teams, because England with Wayne Rooney aren't going to do that anyway. He can be effective in and out of possession."
John Barnes was speaking at the launch of ESPN FC’s partnership with TfL to provide live score updates on the tube throughout the World Cup