In Fischer–Tropsch synthesis (FTS), cobalt carbide (Co₂C) is not a catalytically active material, but rather an undesired cobalt phase associated with low catalytic performance. It is known that Co₂C can be easily transformed back to metal cobalt in a H₂ environment at 220 °C. The transformed metal cobalt (hcp phase) even shows higher catalytic activity in low-temperature FTS, compared with the reduced cobalt metal from the cobalt oxide species. In this study, to obtain Co₂C with high catalytic activity in FTS, we determined the optimum conditions for effective metal cobalt carburization and Co₂C hydrogenation by monitoring the phase transformation of cobalt using X-ray absorption spectroscopy (XAS) and temperature-programmed hydrogenation (TPH). We also verified that the transitions effectively occur under the same conditions as those for FTS (2.0 MPa, 220 °C). Based on the conditions determined for the transitions, the deactivated cobalt catalyst can be completely regenerated in the FT reactor by simply altering the injected gases from syngas to CO and then H₂. Moreover, the regenerated catalyst shows enhanced catalytic performance compared with the fresh catalyst. The selective formation of hcp cobalt metal via carburization and hydrogenation of the spent catalyst was found to be the key for both the improved catalytic activity and the effective regeneration in situ. As a result, the formation of Co₂C, which is mainly considered a nuisance, could provide valuable applications in investigations into catalyst activation and regeneration in FTS.