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 CO 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 CO 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. Fueling fuel production: Biomass conversion into liquid fuel depends on the design of multifunctional catalysts. In the direct conversion of furan‐based aldol adducts into liquid alkanes over a Pd/NbOPO4 catalyst under mild conditions (see scheme), NbOx species played an important role in CO bond cleavage.