Great efforts have been made to convert renewable biomass into transportation fuels. Herein, we report the novel properties of NbOx-based catalysts in the hydrodeoxygenation of furan-derived adducts to liquid alkanes. Excellent activity and stability were observed with almost no decrease in octane yield (>90 % throughout) in a 256 h time-on-stream test. Experimental and theoretical studies showed that NbOx species play the key role in CO bond cleavage. As a multifunctional catalyst, Pd/NbOPO4 plays three roles in the conversion of aldol adducts into alkanes: 1) The noble metal (in this case Pd) is the active center for hydrogenation; 2) NbOx species help to cleave the CO bond, especially of the tetrahydrofuran ring; and 3) a niobium-based solid acid catalyzes the dehydration, thus enabling the quantitative conversion of furan-derived adducts into alkanes under mild conditions.