The polyaniline/bismuth oxybromide (PANI/BiOBr) hybrids materials have been synthesized hydrothermally in the presence of PANI. The PANI/BiOBr hybrids materials were confirmed by X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy and ultraviolet–visible diffuse reflectance spectroscopies. Among the hybrid photocatalysts, PANI/BiOBr-0.2 showed the highest photocatalytic properties for the degradation of rhodamine B (RhB), and the increased photocatalytic properties could be due to photosensitization and the inhibited electron–hole recombination.