The novel NiAl2O4 spinel was used as support to synthesis cobalt catalysts and investigated for Fischer-Tropsch synthesis. The physicochemical properties of the synthesized catalysts (Co/NiAl2O4, Co/Rh/NiAl2O4, Co/Ru/NiAl2O4 and Co/γ-Al2O3) were characterized by XRD, BET, ICP, SEM, FESEM, HRTEM, TPR and TGA analysis before reaction. It was shown the use of novel NiAl2O4 support that was prepared by a modified sol-gel process had a good dispersion. Besides that, Nickel aluminate decreased the interaction of Co and support and resulting in a significant increase in the reduction degree and the catalytic activity. The catalyst of 15Co/0.5Rh/NiAl2O4 shows the highest catalytic activity. It is worth noting that the NiAl2O4 support decreased the CH4 selectivity but enhanced the C5+ selectivity and catalytic stability.