As a promising derivative to achieve efficient utilization of biomass, the preparation of 2,5-bis(hydroxymethyl)furan (BHMF) is of great significance. A kind of carbon nanotubes (CNTs)-supported metallic nickel and nickel oxide catalyst (Ni–NiO/CNTs) was prepared by an impregnation–reduction method and showed excellent catalytic activity in the catalytic transfer hydrogenation (CTH) of 5-hydroxymethylfurfural (HMF) to BHMF. Under optimal conditions, HMF conversion of 100% and BHMF selectivity of 97.6% were obtained using ethanol as the H-donor. Furthermore, it was found that Ni and NiO synergistically catalyzed the conversion of HMF into BHMF after the characterization of the catalyst and factor investigation. Significantly, the ratio of Ni to NiO on the catalyst surface played an important role in the high selectivity of BHMF. To establish the structure–activity correlation, a possible synergistic catalytic mechanism was proposed.