Core-shell composites with titanium dioxide (TiO2) hollow microsphere as the core and graphitic carbon nitride (g-C3N4) as the shell were fabricated via a two-step self-assembly procedure with the assistance of ultrasonic dispersion. The as-prepared composite samples with different g-C3N4 contents (0-20%) were thoroughly characterized and the photocatalytic activity was evaluated by the photocatalytic degradation of Rhodamine B (RhB) in aqueous solution under visible light. A g-C3N4 layer of approximately 80 nm was successfully coated on the surface of TiO2 hollow microspheres with a diameter of 1-3 mu m, forming a heterostructure with close interfacial contact. The TiO2@g-C3N4 composite exhibited significantly enhanced photocatalytic activity as compared with pure TiO2 hollow microspheres. At an optimum weight ratio of g-C3N4 to TiO2 (15 wt.%), the photocatalytic activity of the composite sample was almost 3 times higher than that of reference TiO2 hollow microspheres. Moreover, the results of recycling test indicated that the TiO2@g-C3N4 composite had excellent stability. A possible photocatalytic reaction mechanism of TiO2@g-C3N4 composite was proposed, in which superoxide radical anions played the major role in the oxidation of RhB, and the separation of photogenerated charge carriers across the heterostructure interface inhibited electron-hole recombination, thus enhancing the photocatalytic activity. (C) 2017 Elsevier B.V. All rights reserved.