A feasible route with a dual-templating method including both ice and SiO2 hard templates to fabricate hierarchical porous TiO2 with micro-, meso-, and macro-pores from inorganic/organic metal oxo cluster precursors is proposed. As-prepared TiO2 shows high photocatalytic activity and excellent electrochemical performances. The current strategy can be applied to fabrication of a broad range of metal oxide materials for catalysis and energy related applications.