Molybdenum trioxide materials were prepared in aqueous solutions at 90–95 °C. MoO42−:H+ ratio played important role for crystalline phases of MoO3 samples. The transformation processes of h-MoO3 → α-MoO3·H2O → α-MoO3 were proposed. h-MoO3 microrods and h-/α-MoO3 composite showed good photochromic performances.