Catalytic hydrodeoxygenation of bioderived furans is critically attractive to prepare sustainable fuels. Herein, a novel octanediol-route was developed to produce octane through one-pot conversion of bioderived furans at low temperatures. A 96.6% yield of octane was obtained by catalytic conversion with Pd/C and phosphotungstic acid (HPW). Experimental validation of the novel pathway revealed that octanediol intermediates could be formed through hydrogenolysis of furans before deoxygenation. The spontaneous process of this octanediol-route was thermodynamically confirmed by DFT simulations. In addition, characterization studies suggested that water in the system strengthened the cooperation between metals and acids to facilitate C–O bond scission through the modification and hydrogen transfer of HPW. This work highlights a promising reaction pathway for an efficient HDO catalytic system to obtain alkanes from bioderived furans under mild conditions.