In the absence of injured regular skipper Vaughan, Flintoff will lead England's defence of the Ashes starting next month in Brisbane.
But, Vaughan insists the talismanic all-rounder, who will be expected to produce with the bat and ball as well as captain the side astutely, must not try to do too much on his own.
The Yorkshire batsman fears the pressure could prove too much for Flintoff if he tries to win the five-Test series single-handed.
Flintoff missed the second half of the English season with an ankle injury and, after surgery to cure the problem, he is only just returning to action at the current ICC Champions Trophy in India.
Vaughan told the Wisden Cricketer magazine: "Knowing Freddie, he will want to lead from the front but he's learning fast about the job and he knows he can't be bowling 30 or 40 overs an innings, particularly on Australian pitches. I think he will use himself in short, sharp bursts.
"People have been saying Freddie will have too much on his plate but he wouldn't have put himself forward if he didn't think he could cope.
"For me the fact that he put his hand up to lead England in such a high-pressure series speaks volumes for his character.
"I would tell him; 'Don't try to be someone you're not'. When the pressure is on you, you have to be natural."
Vaughan has not been named in England's Ashes squad as he is still some way from full fitness after surgery on a recurring knee injury.
But he will travel to Australia, where he will continue his rehabilitation in Perth, in the hope of being fit in time for the last two Tests.
Vaughan will be on hand to offer Flintoff advice and he believes England must take the game to Australia if they are to win there for the first time since 1987.
"If you look at the teams who have beaten Australia over the last five or six years, they haven't played a negative game," said Vaughan.
"The Indians did well on their last tour of Australia because they scored heavy runs. You won't beat Australia over the course by playing patient, attritional cricket. You have to try to get ahead of them on day one and stay ahead of them.
"We have a bowling attack that is capable of taking 20 wickets and, whenever you have that, you have a great chance of winning a Test match. We also have batsmen who can score runs on true Australian pitches.
"Most importantly, we have flamboyant players, the type you need to beat Australia. They come hard at you. That's their nature. And you have to match that aggression.
"The Ashes suits our style because we have an aggressive set of players who like to play in that way and will be given the freedom to play in that way."
One player who will be experiencing the cauldron of an Ashes series for the first time is England spinner Monty Panesar.
Panesar emerged as a top-class bowler against Sri Lanka and Pakistan this season and, because he has yet to face Ricky Ponting's side, Vaughan believes he could be England's secret weapon.
"In Australia it is important to have a spinner who can hold an end up on the first day, while the quicks rotate at the other end," Vaughan said.
"Shane Warne does that for Australia but we haven't had anyone able to perform that role for a number of years. Perhaps Monty is the man. It is too early to say. But he certainly looks great on TV."