Ni–ReOx bimetallic catalysts (Ni–ReOx/TiO2) were prepared through a successive impregnation method, which is extremely active in furfural (FAL) hydrogenation to tetrahydrofurfuryl alcohol (THFOL) under mild reaction conditions. For instance, high FAL initial reaction rate (439.4 mmol/g-Ni/h) and THFOL formation rate (80.4 mmol/g-Ni/h) were achieved over Ni–5ReOx/TiO2, which are 13.2 and 6.6 times higher than those of Ni/TiO2, respectively. The unique catalyst reactivity derives from rich Lewis acidic ReOx and intimate electron interaction of ReOx with Ni NPs. Kinetic studies reveal that ReOx decoration decreases the activation barrier of −C═O hydrogenation other than the furan ring. Mechanism studies show that ReOx has a good affinity for C═O and H2 and favors hydrogen spillover and C═O bond activation on Ni, thus reinforcing the synergistic effect of Ni and ReOx. This catalyst is versatile for various furan aldehydes and is relatively stable for 5 times recycling, showing relative potential for industrial application.