Graphene oxide (GO) encapsulated TiO2 core/shell composite microspheres with enhanced photo-activity were synthesized through a series of green and direct chemical bonding reactions involved with dehydration condensation between TiO2 and GO without any modified agents. The as-prepared samples were well characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), micro-Raman spectrometer and Fourier transform infrared spectrometer (FTIR). The photocatalytic activity of the samples was evaluated by photocatalytic decolorization of Rhodamine B (Rh B) aqueous solution at ambient temperature under both UV and visible light irradiation. TEM measurements revealed that the diameter of the as-prepared TiO2@GO core/shell composite microsphere was about 850 nm, while the thickness of the shell is about 5-10 nm. The photocatalytic degradation results showed that the GO-encapsulated TiO2 core/shell structures exhibited an enhanced photocatalytic and excellent recyclability property under the irradiation of UV and visible light for the degradation of Rh B. Crown Copyright (C) 2013 Published by Elsevier B.V. All rights reserved.