The former England goalkeeper, who played for Villa in The Final of 2000, was a close observer when the sides met in the Premier League on Tuesday evening.
That game ended in a 2-1 win for Villa, a much-needed first victory under new boss Tim Sherwood as they battle against relegation.
Aston Villa v West Bromwich Albion
The FA Cup
Sixth Round Proper
5.30pm, Saturday 7 March 2015
Villa Park, Aston Villa FC
Winners receive £360,000 from prize fund
Live on BBC1
And with the Baggies making the short trip back to Villa Park for the Sixth Round tie just four days later, James is intrigued as to how that result will affect his old club.
"The win the other day was more courtesy of performances on the opposition side rather than being great themselves," observed James, who also won The FA Cup with Portsmouth in 2008.
"But you never know what that does to confidence and that was their first [Premier League] win in 13 games, so it will be a fascinating match on Saturday.
"It will be interesting to see what [West Brom boss] Tony Pulis does too with regard to the way his team play and if that win will put a spring in Villa’s step."
James was speaking to TheFA.com on behalf of EE at Wembley Stadium this week, in the same dressing room which was used by Portsmouth during their victory over Cardiff City seven years ago.
And after experiencing first-hand playing for Villa at the national stadium during that Final against Chelsea in 2000, he knows what it would mean to their fans if they could be heading back.
"I want Aston Villa to do well," he admitted.
Highlights of Villa's Fifth Round win over Leicester
"I spent two good years there and I know what the fans are like, with their hunger for more after their success in the European Cup all those years ago.
"It hasn’t really been a legacy in a sense, since the start of the Premier League era and to be honest, I think they’re going to struggle this season.
"But a Cup run can help, so we’ll see what happens on Saturday."
