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β-Bi2O3 decorated graphene nanosheets (β-Bi2O3/GN) were prepared by a facile solution mixing method. The crystal structure, surface morphology, and photo absorbance properties of the products were characterized by XRD, SEM, and UV-VIS diffuse reflection, respectively. Moreover, the effect of graphene content on photocatalytic activity was systematically investigated, and the results indicated that these composites possessed a high degradation rate of Rhodamine B (RhB), which was three times higher than that of bare β-Bi2O3 when graphene content was 1 wt %. This high photocatalytic activity was attributed predominantly to the presence of graphene, which served as an electron collector and transporter to efficiently lengthen the lifetime of the photogenerated charge carriers from β-Bi2O3.