Nonsulfided CeO2‐supported different metal catalysts were synthesized, characterized and evaluated in the hydrogenation of octanoic acid with a batch reactor at the temperature of 280 oC and initial H2 pressure of 3 MPa. The effect of Mo species was revealed by comparing Mo‐doped catalysts with Mo‐free catalysts. The catalytic results show that the CeO2 supported Ni catalyst doped with Mo exhibit much higher catalytic activity and octane selectivity than the catalysts without dopants. Additionally, the influences of Mo and Ni mass ratio on the conversion of octanoic acid and the selectivity of heptane and octane over CeO2‐based catalysts were also discussed. Ni species seemed beneficial for the deoxygenation reaction to form C7 alkane, while the doping of Mo favored the hydrodeoxygenation path to C8 alkane via dehydration‐hydrogenation of the octanol intermediate.