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In this paper, novel TiO 2 /Bi 2 WO 6 heterojunction photocatalysts with hollow microsphere structures were successfully fabricated by a one-pot glucose-assisted hydrothermal route followed by the calcination at 450 °C. The photocatalytic activities of the as-prepared photocatalysts were evaluated on the degradation of rhodamine B (RhB) aqueous solution under visible light irradiation and the results indicated that the as-prepared TiO 2 /Bi 2 WO 6 composite exhibited higher photocatalytic activity than bare TiO 2 and Bi 2 WO 6 . In addition, the TiO 2 /Bi 2 WO 6 composite with TiO 2 loading of 20 wt.% showed the highest photocatalytic activity and retained the high photocatalytic performance after four recycles for the photodegradation of RhB, confirming its stability and practical usability. The enhanced photocatalytic activity of TiO 2 /Bi 2 WO 6 composite was attributed to well matched energy band positions of TiO 2 and Bi 2 WO 6 , which facilitated the efficient separation of photogenerated electron–hole pairs and thereby led to the increasing photocatalytic activity. On the basis of calculated energy band positions, the results of photoluminescence (PL) and active species trapping experiments, the mechanism of the obviously enhanced photocatalytic performance was proposed. [ABSTRACT FROM AUTHOR]