ABSTRACTThe metastable phase of well-faceted, hexagonal, prism-like molybdenum oxide hydrate (MoO3·0.55H2O) was successfully synthesized by evaporating molybdic acid solution prepared through cation membrane electrolysis of Na2MoO4·2H2O aqueous solution. The obtained crystals were characterized by X-ray diffraction (XRD), thermogravimetric (TG), scanning electronic microscopy (SEM) and photoluminescence (PL) spectrophotometry. The as-prepared MoO3·0.55H2O rods were of 2–4 μm in width and 5–12 μm in length. The MoO3·0.55H2O microrods displayed photoluminescence properties at room temperature and were transformed into stable orthorhombic α-MoO3 after air annealing at 380 °C. Moreover, the influence of temperature factor on the phase transformation process, morphology and photoluminescence properties of MoO3·0.55H2O was investigated in detail.