TiO2 nanospheres were prepared via hydrolysis of titanium glycolate precursor. TiO2 nanospheres exhibited a mesoporous structure with a high surface area. TiO2-NSs electrode was used as an anode for aqueous aluminium-ion batteries. TiO2-NSs electrode exhibited superior rate performance with a high capacity. TiO2-NSs showed better electrochemical performance than TiO2-P25.