Former Manchester City ace could not resist a dig at rivals.
The England assistant and esteemed pundit could do little as Luis Enrique's side ran riot, with Lionel Messi scoring a hat-trick, and Luis Suarez adding four.
This was the latest of a number of poor results for Neville, and former Manchester City player Rodney Marsh could not resist a dig.
Marsh took to Twitter to suggest Neville would be perfect for the Manchester United manager's job to replace Louis van Gaal.
So Gary Neville is the next manager of Manchester United, perfect he'll fit right in .....— Rodney Marsh (@RodneyMarsh10) February 3, 2016
Neville told SkySports back in December after his surprise appointment at Valencia that he did not see himself becoming manager of United at any point in the future.
Even if he had done superbly in Spain, his inexperience would have made him a long shot, but now there is little chance the Red Devils will be seeking him out.
United are in fifth place in the Premier League, and at risk of not qualifying for next season's Champions League, a competition they have already exited this season.
In fact his spell at Valencia may have been enough to put him off management for good...