A series of hierarchical pore molecular sieves (HPMSs) with pore size up to 6.0 nm were prepared using triblock copolymer (P123) as mesoporous template agent and characterized by N2 adsorption-desorption. Cobalt-loaded catalysts were prepared by impregnating cobalt nitrate onto HPMSs and characterized by X-ray diffraction and scanning electron microscopy. The result indicates that mesopore size of HPMS increased along with the increment of the amount of P123. The selectivity of the catalysts for Fischer-Tropsch synthesis was evaluated in a fixed-bed reactor, and the results show that the selectivity of C12+ hydrocarbons is increased with the increment of the pore size.