'England should consider Brook when Stokes is out'
All-rounder Stokes is missing the final Test against India at The Oval because of a shoulder injury, with vice-captain Ollie Pope deputising.
The 34-year-old's recovery is likely to take around eight weeks, before the Ashes series in Australia beginning in November.
Yorkshire's Brook became England's white-ball captain earlier this year, winning his first series in full-time charge against West Indies.
"Harry Brook, to me, looks a leader. He looks a born leader," Vaughan told the Test Match Special podcast.
"If Ben Stokes is injured in the future can't Pope stay as vice-captain and Harry Brook gets the leadership role?"
Crawley falls late as India take upper hand
'England chasing history after backing themselves into a corner'
Vaughan is regarded as one of the finest captains to have led England, masterminding the famous 2005 Ashes series win. He won 26 of his 51 Tests in charge between 2003 and 2008.
He added: "I look at someone like Ollie Pope, who looks a fantastic vice-captain. He is brilliant person to have next to the captain to come up with ideas. Sometimes vice-captains aren't brilliant captains.
"Marcus Trescothick was a magnificent vice-captain for me but you wouldn't to give him the captaincy."
Pope, 27, is leading England in a Test for the fifth time. He previously stood in when Stokes had a hamstring injury last year.
Under Pope, the home side face an uphill task to win the decisive fifth Test. After being set 374 to beat India, a target that would represent their second-highest successful chase in a Test, they closed the third day on 50-1.
On Saturday, without the injured Chris Woakes, England were left relying on trio of seamers Gus Atkinson, Josh Tongue and Jamie Overton.
Though they were eventually able to dismiss India for 396 in their second innings, England were hampered by six dropped catches.
"It is not Ollie Pope's fault England are in this position. It is the dropped catches," said Vaughan.
"There were a couple of times he nipped off the field, it might have been for a comfort break, but it looked like he was going off for tactical advice.
"I don't know well enough and am not in the dressing room. I just want the best captain who is the best leader leading the England side. I don't think a good vice-captain will necessarily be a good captain."
England's highest run chase of 378 came against India three years ago at Edgbaston. They also successfully overhauled 371 against the same opponents to win the first Test of this series at Headingley.
"We're pretty chilled," said Tongue. "There won't be any over-thinking about it.
"I got asked the same question at Headingley. I don't see why we can't chase down these runs.
"How we play is very positive and exciting. With the batting line-up we've got, I can't see why we can't give it a good go."
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