Neville won 85 caps for his country and played in two World Cups - but he retired with a sense of frustration that England had under-achieved during his era.
The former Manchester United full-back has admitted there were times when he reflected on his international career as "a massive waste of time".
Interim head coach Stuart Lancaster is attempting to launch a new era for English rugby, with the ultimate goal being victory on home soil in the 2015 World Cup.
Lancaster turned to Neville and England rugby league captain Jamie Peacock to help restore a sense of pride and honour in the squad following last year's failed World Cup campaign New Zealand.
"Gary Neville never turned down playing for his country. He played 85 times, he is England's most-capped full-back," Lancaster said.
"Speaking to him, he was frustrated because he never felt he achieved with England what he wanted to achieve.
"He wants to help the players understand (what is possible) when you get it right, when you are playing for your country and the nation is behind you.
"When it was Euro '96, three lions on the shirt, how powerful was that? We all felt it. He wants to help our team get that feeling.
"When I asked if he would do it, he said it would be an honour.
"That is what I have been trying to say to the players. I probably see it more because I have come from the grassroots game and I have seen what impact becoming an international coach has had on people around me.
"I am trying to remind the players of the pride and the honour and the standing of being an international rugby union player in this country. It is massive."
The England squad will also be addressed by Hugh Morris, the managing director of England cricket, and Kevin Sinfield from Leeds Rhinos on what makes elite teams.
Neville will be joined by Peacock and their message reinforced by Simon Brown, a former British Army corporal who was shot in the face while serving in Basra in 2006.
Brown said before meeting the squad that his message would be: "Be proud to wear your national shirt.
"How many of us wouldn't offer up limbs to have the opportunity to put on our national shirt and you guys have that opportunity."
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