James defied Villa with a string of fine saves as the Midlands club increased their unbeaten run to six matches with their fourth successive draw at Villa Park.
But it was James who took the honours on his return to Villa Park as he produced an outstanding display and in the process singlehandedly frustrated his old club.
The highlight of his performance came in the 65th minute when Gabby Agbonlahor twisted and turned before firing in a rising drive which James finger-tipped over the bar.
Villa are finishing the season as they started with a good unbeaten run as this was their sixth successive game without a defeat.
The outcome was hardly a surprise as Pompey last won at Villa Park in 1975. They have only won four of the 35 encounters and this is the eighth draw between the two clubs.
But Portsmouth's first-half performance was hardly connected with a side with European aspirations. They never moved into top gear and generally gave Villa an easy ride.
There was no drive and as a result they failed to get a single attempt on target as Olof Mellberg and Martin Laursen effectively shut out all their attacks.
Villa were slightly the better team but they too were also off the pace. It might have been a different story if Craig Gardner, preferred to a seemingly out of favour Gavin McCann, shot straight at James.
Patrik Berger's finishing also left something to be desired when he blasted high and wide, while another Gardner effort late in the half was blocked much to the frustration of manager Martin O'Neill, who relentlessly paced up and down throughout the game.
Sol Campbell was a major stumbling block and Portsmouth's success has been generated by his stalwart defensive play when he accords the opposition few opportunities.
John Carew became the latest striker to be frustrated by Campbell's domination although the big striker did manage to get an effort on target when he shot on the turn only to see James make another confidence-boosting save.
The longer the game went on the more it became obvious that Portsmouth were quiet happy with a goalless stalemate.
Matt Taylor didn't produce their first shot on Villa's goal until the 64th minute and even that went into the side netting.
The introduction of three young players, Luke Moore, Ashley Young and Shaun Maloney gave Villa a freshness in attack, but Portsmouth's defence remained rock solid with Linvoy Primus giving Campbell sound support.
It was Young who carved out Villa's best chance late in the game, but skipper Gareth Barry screwed his shot wide with only the formidable James to beat.