Nanosized mesoporous anatase TiO2 particles have important applications in high-performance lithium ion batteries and effi cient photocatalysis. In contrast to the conventional synthesis routes where various soft or hard templates are usually employed, the direct growth of uniform mesoporous anatase TiO2 nanospheres on graphene sheets by a template-free selfassembly process is presented. Compared to the conventional mesoporous anatase particles consisting of polycrystalline TiO2, the microstructure of obtained mesoporous anatase nanospheres on graphene sheets is singlecrystal- like. The growth mechanism, lithium ion battery performance, and photocatalytic activity of the resultant mesoporous anatase TiO2 nanospheres/ graphene composites are thoroughly investigated. In comparison to the reference TiO2, the composite shows substantial improvement in lithium specifi c capacity from 1 C to 50 C, and photocatalytic removing organic pollutant and hydrogen evolution. More strikingly, the specifi c capacity of the composite at the rate of 50 C is as high as 97 mA h g(-1), 6 times higher than that of the reference TiO2.