Microplasma-induced non-equlibrium electrochemistry is employed to prepare soluble and crystalline Mo species in a water-deficient and extraneous ionic-salt-free ethanol electrolyte. The anodization of Mo in absolute ethanol is found to produce Mo oxyethoxide in the liquid ethanol phase, along with a small montage of mixed hexagonal and orthorhombic MoO3 crystals. The evolution of Mo species in solid and liquid phases is characterized to study the crystallization of MoO3 crystal and the formation of blue spherical Mo polyoxometalates (POMs) after extended aging (Crystal Growth & Design 19, 2019, 5249).