Supported molybdenum/molybdenum‐phosphides as inexpensive catalysts for bio‐oil hydrodeoxygenation (HDO) were in‐house prepared using different support materials, i.e., Al2O3, activated carbon (AC), MgAl2O4, and Mg6Al2(CO3)(OH)16. The HDO activity of these catalysts were investigated using a 100 mL bench‐scale reactor operating at 300°C with an initial hydrogen pressure of 50 bar for 3 h with a pyrolysis oil (PO). The catalytic efficiencies for bio‐oil HDO for the catalysts were compared with the expensive but commercially available Ru/C catalyst. Addition of small amount of P to the Mo catalysts supported on either AC and Al2O3 led to increased degree of deoxygenation (DOD) and oil yield compared with those without P. MoP supported on AC (MoP/AC) demonstrated bio‐oil HDO activity comparable to the Ru/C catalyst. Furthermore, three AC‐supported metal phosphides for PO HDO were compared under the same conditions, and they were found to follow the order of NiP/AC > CoP/AC > MoP/AC. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3664–3672, 2016