The core-shell-structured Co-Z@TiO2(N-2+O-2) catalyst, which was prepared by subsequent pyrolysis and calcination from precursor ZIF-67 coated by amorphous TiO2, was applied in Fischer-Tropsch synthesis (FTS). Compared with Co-Z@TiO2 catalyst, which was directly calcinated in air (Co-Z@TiO2(O-2)) or pyrolyzed in N-2 (CO-Z@TiO2(N-2)), the Co-Z@TiO2(N-2+O-2) catalyst showed better dispersion, easier reducibility, and optimal metal cobalt particle size (8.4 nm) due to the intermediate pyrolysis treatment and core-shell structure. The Co-Z@TiO2(N-2+O-2) catalyst exhibited high cobalt time yield (14.84 mu mol(CO).g(Co)(-1).s(-1)), high selectivity to C5+ (81.5%), and low selectivity to low carbon hydrocarbon (CH4 (12.7%) and C-2-C-4 (5.8%)). The core-shell structure could enhance diffusion limitations to transform intermediate products into heavier hydrocarbons. After 110 h of evaluation, the Co-Z@TiO2(N-2+O-2) catalyst still maintained good catalytic performance and cobalt particle size distribution.