A three-dimensionally ordered macroporous (3DOM) ZrO2 support with mesoporous walls was prepared using colloidal crystal PS spheres as templates and was used to prepare the 3DOM Co/ZrO2 catalyst via incipient wetness impregnation method to support active metal cobalt on zirconia with 3DOM structure. Two other cobalt catalysts supported on zirconia materials with different pore structure were also prepared as references. The N-2 adsorption/desorption, XRD, SEM, TEM, TPR, hydrogen chemisorptions and XPS techniques were used to characterize the support and (or) catalyst. The 3DOM zirconia support with interconnected networks of spherical voids was beneficial to the dispersion of Co species with less aggregation. The as-obtained 3DOM Co/ZrO2-3 catalyst showed good dispersion and high reducibility of cobalt species, which led to more cobalt surface active sites and thus an excellent catalytic performance for the Fischer-Tropsch synthesis (FTS) reaction. The hydrocarbons selectivity of the catalyst greatly depended on the pore structure of the 300M ZrO2 support. The macropores, which provided channels for rapid molecular transportation, were in favor of the enhancement of C5+ selectivity. However, the small pores within the walls of 3DOM entities limited the diffusion efficiency of the reactants/products and contributed to the selectivity of methane. (c) 2012 Elsevier B.V. All rights reserved.