In this study, we present flower-like rutile TiO2 superstructures could be successfully fabricated by taking advantage of a facile solution-phase approach at room temperature. The surface area and amount of surface hydroxyl groups on rutile TiO2 superstructures could be tuned by calcing the sample at different temperatures. Photocatalytic experiments demonstrated the room temperature synthesized rutile TiO2 superstructures exhibited excellent photocatalytic activity compared to that of the calcined ones, which were thought to be mainly attributed to its large surface area. We further studied the photocatalytic process of RhB on different rutile TiO2 superstructures by active species trapping experiments and analyzed the relationship between the major active species and the main influencing factors responsible for the photocatalytic performance for elucidating a surface area and surface charge cooperative photocatalytic mechanism. (C) 2014 Elsevier B. V. All rights reserved.