Cu/CaO catalysts with fine-tuned Co-doping for excellent catalytic performance of furfural (FAL) hydrogenation to furfuryl alcohol (FOL) were synthesized by a facile wetness impregnation method. The optimal Co1.40Cu1/CaO catalyst, with a Co to Cu mole ratio of 1.40:1, exhibited a 100% FAL conversion with a FOL yield of 98.9% at 100 °C and 20 bar H2 pressure after 4 h. As gained from catalyst characterizations, Co addition could facilitate the reducibility of the CoCu system. Metallic Cu, Co-Cu alloys, and oxide species with CaO, acting as the major active components for the reaction, were formed after reduction at 500 °C. Additionally, this combination of Co and Cu elements could result in an improvement of catalyst textures when compared with the bare CaO. Smaller catalyst particles were formed after the addition of Co into Cu species. It was found that the addition of Co to Cu on the CaO support could fine-tune the appropriate acidic and basic sites to boost the FOL yield and selectivity with suppression of undesired products. These observations could confirm that the high efficiency and selectivity are mainly attributed to the synergistic effect between the catalytically active Co-Cu species and the CaO basic sites. Additionally, the FAL conversion and FOL yield insignificantly changed throughout the third consecutive run, confirming a high stability of the developed Co1.40Cu1/CaO catalyst.