Display omitted •Mesoporous TiO2 was prepared using an evaporation-induced self-assembly method.•The obtained TiO2 had hexagonal mesostructure with highly crystalline anatase phase.•Mesoporous TiO2 exhibited high sunlight-driven photocatalytic activity in dye degradation.•The charge-dependent photocatalytic behaviour of the mesoporous TiO2 was investigated. The development of new strategies and photocatalytic materials for practical environmental solutions remains a great challenge, particularly due to the large energy demands associated with various remediation processes. In this paper, we report the fabrication of self-assembled ordered mesoporous TiO2 with highly crystalline anatase structures as well as high surface area, and characterize their photocatalytic performance on the degradation of three typical dyes, including anionic methyl orange, cationic methylene blue, and neutral rhodamine B driven merely by sunlight. The results show that the dye photodegradation strongly depends on the charging state of both mesoporous TiO2 surface and dyes, which can be adjusted by the pH value of the solutions. Such charge-dependent photocatalytic functionality of mesoporous TiO2 can thus be exploited for highly efficient and selective dye photodegradation.