Hierarchical tungsten oxide assemblies such as spindle-like, flowers with sharp petals, nanowires and regular hexagonal structures are successfully synthesized via a solvothermal reduction method by simply adjusting the reaction conditions. On the basis of the experimental results, it is determined that the reaction time significantly influences the phase transition, microstructure and photocatalytic activity of the prepared samples. The possible mechanisms for the phase transition and morphology evolution process have been systematically proposed. Moreover, the as-prepared products exhibit significant morphology-depended photocatalytic activity. The flower-like W18O49 prepared at 6 h possesses large specific surface area (150.1 m²g^-1), improved separation efficiency of electron-hole pairs and decreased electron-transfer resistance by the photoelectrochemical measurements. As a result, the flower-like W₁₈O₄₉ prepared at 6 h exhibits the highest photocatalytic activity for the degradation of Methyl orange aqueous solution. The radical trap experiments showed that the degradation of MO was driven mainly by the participation of h⁺ and •O²⁻ radicals.