The 31-year-old could make his debut against Scotland, after finishing as the joint-leading English goalscorer in the Premier League last season.
Neville does not think that the Southampton forward will be fazed by the occasion.
"We talked about Rickie Lambert, but the opportunity has now come for Rickie and we are looking forward to seeing him," Neville told Sky Sports News.
"At the end of the day it's there, the opportunity for everyone to take it, and hopefully he will get his opportunity against Scotland on Wednesday.
"I think he has got the confidence having watched him quite a lot of times last year. He has certainly got the confidence to not be faxed by the occasion and has a good arrogance a forward needs."
England take on Scotland at Wembley at 8pm on Wednesday.