Sunderland goalkeeper Pickford was vital to the result for the Lilywhites who ended the Championship clash with nine men following red cards to Joe Garner and Bailey Wright.
Preston took the lead in the 10th minute when Daniel Johnson produced a lovely curling effort to beat a despairing Martinez with the Arsenal gloveman unable to deny the Jamaican winger.
Martinez then acrobatically snuffed out a flying effort from Garner before the Lilywhites striker was shown a red card for a rough aerial challenge on Danny Batth.
Pickford came into it to thwart Jed Wallace twice in the second half before Australian defender Wright was given his marching orders for a second bookable offence, this one on Dominic Iorfa.
The 21-year-old Black Cats keeper had a mountain of work in front of him as Wolves pressed for an equaliser and was at his best to deny Batth's near-post header in the 90th minute before Preston's resistance was broken by a stunning Kevin McDonald curler from 25 yards in the first minute of injury-time.
Pickford's performance throughout, particularly late with two less men on the pitch, was brilliant and landed him Man of the Match honours from Preston:
90+2' Jordan Pickford is selected as the George Banks Jewellers man of the match. #PNElive 1-1
— pnefc (@pnefc) September 26, 2015
Check out the match highlights below:
Liverpool youngster Sheyi Ojo came on as a second-half sub for Wolves while Manchester United striker Will Keane started for Preston before making way for Jordan Hugill in the 65th minute, when Oyo entered the field of play.
The draw has sitting 22nd on the tier two table with seven points from nine matches as Wolves dropped to 16th.