The presidential run-off, originally due to be held on Sunday but delayed due to organisational problems, will see two former premiers -- Anicet Georges Dologuele and Faustin Archange Touadera -- compete for election.
A presidential decree said a December 30 legislative election annulled due to irregularities will be held along with the runoff on February 14.
The elections have been widely seen as turning a page on the worst sectarian violence in the traditionally unstable and dirt poor nation.
Dologuele, a 58-year-old former central banker, came to be known as "Mr Clean" after his attempts to bring transparency to murky public finances during his time as premier.
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Touadera, also 58, is a former maths professor who served as prime minister under disgraced ousted president Francois Bozize.
He was considered an outsider among the 30 candidates running for the top job.
The announcement comes after the country's top court on Monday annulled last month's first-round legislative vote over "irregularities", but said the second round of the presidential poll could go ahead.
Nearly two million people were eligible to vote in the polls, seen as the way out of more than two years of sectarian bloodshed that has forced about one in 10 of the nation's 4.9 million people to flee their homes.
The violence set mainly Muslim rebels against vigilantes from the Christian majority, with civilians the main victims.