Co-promoted Cu/ZnO catalysts were studied for Fischer-Tropsch synthesis (FTS). All catalysts were prepared by the co-precipitation method, having the mass ratio of Co:Cu:Zn=0 (unpromoted), 0.05, 0.5:1:1, and characterized by X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), including X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). From XRD and XAS, the results confirmed the phase transformation of CuO to Cu foil and Co3O4 to Co foil in Co-promoted catalysts after reduction. After FTS reaction testing, the Co-promoted catalysts showed the decrease in methanol selectivity of 15 and 1.6% for 0.05Co-Cu/ZnO and 0.5Co-Cu/ZnO, respectively, and the increase in C5-C15 selectivity during 30 h of reaction.