^ A. River Plate was originally qualified as runners-up of the 2013 Campeonato Sergipano. Because of their request to be absent for 2 two years of the Campeonato Sergiano due to financial problems, Lagarto earned their spot.
A draw by CBF held on January 10, 2014 set the matches for this round. The 81 qualified teams were divided in eight pots (A-H) with 10 teams each. They were divided based on the CBF Rankings and the matches were drawn from the respective confronts: A x E; B x F; C x G; D x H. The lower ranked teams of each match will host the first leg. Before the Round of 16 there will be another draw including the six teams that will play the 2014 Copa Libertadores.
A draw by CBF was held on August 18 to set the matches for this round. The 16 qualified teams were divided in two pots. Teams from pot 1 are the ones who competed at the 2014 Copa Libertadores plus the two highest CBF ranked teams qualified via the Third Round. Pot 2 is composed of the other teams that qualified through the Third Round. Each pot was divided into 4 pairs according to the CBF ranking. That division makes sure that each team within a pair will not face each other before the finals as they will be placed in opposite sides of the bracket. There was a draw to decide the home team of the round of 16. The following stages will have other draws to determine the order of the matches as the tournament advances.
Note 1: Due to racist chants against Santos' player Aranha by Grêmio fans in the first leg, the STJD suspended the second leg scheduled for September 3 and removed Grêmio from the tournament, thus automatically qualifying Santos to the next round.