"I am surprised that Paul O'Connell got the captaincy ahead of Brian O'Driscoll," said de Villiers, whose men take on the Lions on June 20, 27 and July 4 of this year.
"This is a huge accolade for Paul O'Connell and it will come with great responsibility.
"O'Driscoll was the most successful captain in the Six Nations and captained the Lions four years ago.
"Having said that, O'Connell is the captain of Munster and has also captained Ireland at Test level and we will not underestimate his leadership capabilities."
With O'Connell's appointment and the rest of the Lions squad now out in the open, de Villiers says he and his fellow coaches can now further their own planning ahead of the three-match Test series in Durban, Pretoria and Johannesburg.
"I am looking forward to the Test series," added de Villiers, who coached the Boks to successive wins over Wales, Scotland and England in November last year.
"Now that we know the make-up of the Lions squad we will be able to advance our preparations in terms of our analysis of their strengths and weaknesses, how we expect them to play and how we must prepare for the three Tests.
"A Lions tour is always a momentous occasion and 2009 will be no different. Our guys know the magnitude of the task that lies ahead and they know the expectation that there is, especially in view of the disappointments of 1997."