The characteristics of an atmospheric pressure glow discharge with a metal cathode and water anode and underwater plasma were compared during the formation of nanostructured molybdenum oxide. The electrical and spectral characteristics of both types of plasma were studied. In both cases, the emission continuum presents in the spectrum because of sputtering the electrode material. The analysis of obtained powder was performed using scanning electron microscopy and x-ray diffraction. Results showed that the mixture of molybdenum oxides is formed for both plasmas.