• 2-Methyltetrahydrofuran production from furfural using a trimetallic catalyst. • Cu nanoparticles on the Hβ surface became smaller after doping Ni or Re. • The adsorption configurations of reactants on the catalyst were determined. • The hydrogenation and hydrodeoxygenation sites of the catalyst were determined. The direct conversion of furfural (FUR) to 2-methyltetrahydrofuran (2-MTHF) was investigated over a trimetallic CuNiRe/Hβ catalyst. Under optimal reaction conditions at 240 °C under 3 MPa H 2 for 1 h, almost complete conversion of FUR and high-yield of 2-MTHF (81%) was achieved. This is the highest yield reported for the direct conversion of FUR to 2-MTHF. HR-TEM demonstrated that the growth of Cu nanoparticles (NPs) on the surface of Hβ was inhibited after loading Ni or Re resulted in the smaller Cu particle size and better hydrogenation and hydrodeoxygenation activity. H 2 -TPR characterization exhibited that the reducibility of bimetallic and trimetallic catalysts was higher than that of monometallic catalysts. NH 3 -TPD explained that Hβ acid sites mainly contributed to FUR deoxygenation. The adsorption configurations of FUR, furfuryl alcohol (FOL) and 2-methylfuran (2-MF) on the catalyst were revealed by ATR-IR. Catalyst evaluation and control experiments proved that FUR was first hydrogenated to FOL, followed by hydrodeoxygenation to 2-MF, and finally hydrogenated to 2-MTHF catalyzed by the combination of three metals.