Catalysts for reduction of tetrahydrofuran-2-carboxylic acid (THFCA), which can be synthesized from furfural via oxidation and hydrogenation, were explored among the combinations of noble metal and reducible metal oxide supported on SiO2. Rh-WOx/SiO2 catalysts showed activity in C-O hydrogenolysis at 2-position of THFCA (to δ-valerolactone and 5-hydroxyvaleric acid) and higher yield ratio of these C-O hydrogenolysis products to carboxylic acid hydrogenation products than other bimetallic catalysts. The activity of Rh-WOx/SiO2 catalysts was highest at W/Rh = 0.25 mol/mol. XRD, TPR, CO adsorption and XAFS characterizations showed that the Rh-WOx/SiO2 (W/Rh = 0.25) catalyst contained Rh metal particles with surface modification with isolated W2+ oxide species. The mechanism that hydride-like species formed on Rh atom attacks the C atom at the α-position (2-position) of adsorbed carboxylate on W atom is proposed based on the similar kinetics and similar catalyst structure to Rh-MOx/SiO2 (M = Re, Mo) which is known to be active in THFA hydrogenolysis to 1,5-pentanediol.