Everton full-back Baines came in for some criticism for the performance that he put in against Italy at the weekend, with some having claimed that Roy Hodgson should have included the experienced Ashley Cole in his squad.
However, Neville is a former teammate of Baines and he believes that the 29-year-old will prove his quality in what is a vital fixture for the Three Lions.
"Leighton Baines got some stick for his performance against Italy but I think he will show against Uruguay why he is England's best left-back," Neville wrote in his BBC Sport column.
"Cole was possibly the best left-back in the world for a 10-year period but that time has gone. Hodgson is building a team with future tournaments in mind which is why Everton's Baines and Southampton teenager Luke Shaw got the nod.
"The criticism will not have bothered Baines, though. He is somebody I know well from our time together at Everton and I think he will grow into this tournament from now on - starting with him playing a key attacking role in Sao Paulo on Thursday."
Baines has been capped on 25 occasions by England, during which time he has scored one goal.