The Mo-doped Co-B amorphous catalyst (Co-Mo-B) were prepared by chemical reduction of mixed CoCl2 and Na2MoO4 with KBH4 in aqueous solution. This catalyst exhibited excellent activity and nearly 100% selectivity to furfuryl alcohol (FFA) during liquid phase hydrogenation of furfural (FFR); the promoting effect of Mo-dopant on the hydrogenation activity was investigated and the optimum Mo/(Mo + Co) molar ratio (X-Mo) was determined as 0.064. Pretreatment of the Co-Mo-B amorphous catalyst resulted in the abrupt decrease in its hydrogenation activity owing to both the gathering of catalyst particles and the crystallization of the catalyst. It was found that the Mo-dopant in the Co-Mo-B catalyst was mainly present in the form Of MoO3. Thus, its promoting effect could be attributed to both a dispersing effect that resulted in the higher surface area and the acidic property Of MoO3 that was favorable for the adsorption of carbonyl group in FFR molecules, The superior activity of the Co-Mo-B amorphous catalyst over its corresponding crystallized counterpart could be attributed to both the structural effect and the electronic effect.