A layered Mo doped Pr0.5Ba0.5MnO3−δ (Mo-PBMO) double perovskite oxide was prepared by a modified sol–gel method and the properties of the fabricated material are characterized by various technologies. The results of X-ray diffraction (XRD), H2-temperature programmed reduction (H2-TPR), NH3-temperature programmed desorption (NH3-TPD), and thermogravimetric analysis (TGA) demonstrate that the treatment in reducing atmosphere at high temperature lead to a significant phase transformation of the material to a single cubic phase as well as with the Mo in multiple oxidized states. Such character leads to the production of large amount of oxygen deficiency with facilitated oxygen diffusion. The electrochemical performance tests of half-cell and single cell SOFCs exhibit the promoted effect of Mo on catalytic activity for the oxidation of H2 and CH4, indicating that Mo-PBMO could serve as an anode material candidate for SOFCs.