Citric acid was used to selectively extract cobalt from limonite-type laterite ores in the presence of ammonium bifluoride. The results show that ammonium bifluoride enhances the leaching of cobalt by citric acid, and 84.5% cobalt is extracted from a laterite ore containing 0.13% Co when leached at ambient temperature for 2 h with 30 g/L citric acid and 10 g/L ammonium bifluoride. Pyrolusite is reduced by citric acid during leaching, cobalt intergrown with which is liberated and subsequently chelated by the citric acid. The extraction of cobalt is enhanced in the presence of ammonium bifluoride because the matrix of silicate minerals is destroyed by ammonium bifluoride and the adsorbed cobalt is subsequently liberated.