Brought in as a replacement for injured all-rounder Andrew Flintoff, 24-year-old Pietersen - who has yet to play Test cricket - was England's star in their 4-1 One-day series defeat in South Africa concluded last month.
In all he scored 454 runs with three centuries including an unbeaten 100 off 69 balls, the quickest three figure score by an England batsman in a Limited Overs International, at East London.
He achieved this against a constant barrage of verbal abuse from home fans angered that Pietersen, born in Pietermaritzberg, had turned his back on South Africa to play for England, his mother's country, because of what he perceived as a racial quota policy favouring black players which was hampering his prospects.
"Kevin Pietersen will cause a few headaches by the way he's played in the One-dayers," Vaughan said in London on Wednesday. "He's got a huge amount of talent.''
Vaughan said it was the former Natal player's character, as much as his ability, which had made him think Pietersen, who this season will play County cricket for Hampshire after moving from Nottinghamshire, could prosper against world champions Australia.
"He's got a huge amount of talent but the three hundreds he scored, he also showed tremendous character considering the pressure he was under," Vaughan explained.
Flintoff, who has yet to play a Test against Australia, is currently recovering from a bone spur operation to his left ankle.
The prospect of the hard-hitting Lancastrian and the equally aggressive Pietersen linking up in England's Test-match middle order has excited fans during the British winter.
"If those two get going there will be a need for helmets on in the crowd," said Vaughan.
"They are very destructive and can take the game to the opposition. When you play Australia you need character and that little bit of arrogance about you and Kevin has those attributes."
England have won four straight Test series victories during the past 12 months as well as setting a new national record of eight successive wins.
However, Australia have won all eight Ashes series since 1989 and remain strong favourites to continue that run ahead of the first Test at Lord's starting on July 21.
"You can play against a number of teams and win but the question you get asked the most is 'how are you going to do against Australia?' That question is going to be answered this summer," Vaughan added.
"It is a challenge I am really looking forward to because when you face the biggest challenges you have to relish it and I am sure the team will be thinking the same way.
"We realise we are up against the best team in the world at this moment in time and probably the best team that has ever played.
"But we won't change our approach, we are going to play positive, attack and try to keep them under pressure for the whole of the summer."