The efficient hydrogenolysis of dibenzofuran (DBF) was investigated at 360 degrees C and atmospheric hydrogen pressure with Co/MoO3 catalysts. All catalysts selectively cleaved the C-O bond and thus effectively transformed DBF to biphenyl (BP) at relatively moderate conditions. A strong promotional effect in the catalytic activity was observed over the Co/MoO3 catalyst with the optimal Co content of 3 wt %, as evidenced by the decreasing activation barrier which was resulted from Co-facilitated increase of active Mo species and acidic sites. The best catalytic activity was realized with almost 100% yield of BP over Co/MoO3. During 300 h of catalyst life test, the MoO3 and Co/MoO3 catalysts underwent a gradual deactivation because of the over-reduction of Mo species and carbon deposition as evidenced by the characterization of X-ray diffraction, X-ray photoelectron spectroscopy, Raman, thermogravimetric analysis-mass spectrum, and transmission electron microscopy. However, the deactivated catalyst can be regenerated with simple calcination using O-2, without losing its initial activity. Characterization studies demonstrated that the formation of MoOxCyHz played an important role in stabilizing Mo species by preventing over-reduction to inactive Mo4+ species.