The structure and catalytic properties of BiCeVMoO catalysts with different composition for selective oxidation of propane have been investigated. It has been shown that bismuth may be substituted by a low amount of cerium while the Scheelite structure of BiVMoO remains unchanging. With the increasing of Ce (Ce/(Ce + Bi) > 0.15), new phases of CeVO 4 and Ce 2(MoO 4) 3 formed. The cerium which probably entered into the lattice of BiVMoO promotes the forming of acrolein, and the selectivity to acrolein increased to a maximum at Ce/(Ce + Bi) atomic ratio = 0.15 (45 mol% at ∼30 mol% propane conversion). Further increasing Ce content results in further oxidation of propylene and acrolein to CO x due to the strong oxidative ability of catalysts. The proper amount of introduced cerium, which probably occupied the lattice sites of Bi 3+ enhanced the oxidative ability of catalysts moderately by increasing the activity and the amount of surface active oxygen species.