De Villiers will skipper Boks in Test series.
The 31-year-old, who has won 72 caps for the Springboks, has initially been handed the role until the end of the England tour, which begins with Saturday's first Test in Durban.
The Western Province back, who succeeds the now-retired John Smit, was preferred to the other strong candidate for the role, Pierre Spies of Meyer's former club Blue Bulls.
New coach Meyer, who named a 32-man squad at the weekend, will review the position at the end of the series with two other potential captains, Schalk Burger and Juan Smith, presently out injured.
Meyer said: "Jean's leadership qualities are well established and he has always impressed me with his leadership on and off the field.
"I've also been impressed by the way he's led a young and inexperienced DHL Stormers team in Vodacom Super Rugby this year.
"Jean commands respect from everyone in South African rugby and in the short space of time we've worked together, he has shown that he understands what we want to achieve on the field.
"He will be surrounded by a core of strong leaders in the squad and we have the utmost faith in them."
De Villiers is the second most experienced player in the Springboks squad, behind 74-cap Bryan Habana.
De Villiers has scored 19 tries for South Africa.
Meanwhile Wales defence coach Shaun Edwards is confident his players have no hang-ups about the nation's poor record Down Under as they seek a first away win over a Southern Hemisphere side in 25 years.
Edwards led the advance guard of 16 players to Brisbane to prepare for this month's three-Test series against Australia - the opener is on Saturday - and believes the team will have no problem channelling their frustration at recent results on the Wallabies' turf.
The 45-year-old said: "The Welsh statistics against any team in the Southern Hemisphere don't make good reading, especially away from home.
"We have to go out and prove we are mentally strong enough to win down here.
"This team wants to make its own history."
* LEADER: Jean de Villiers, right, will skipper South Africa in their three England Tests