Sheet-like agglomerates β-Bi2O3 were synthesized via an extraction-precipitation stripping-decomposition method using a leaching solution of bismuthinite as raw materials in acidic chloride media. Phase form of as-prepared Bi2O3 was confirmed by X-ray diffraction（XRD） and its morphology was observed by scanning electron microscope（SEM） and transmission electron microscope（TEM）. Moreover, photocatalytic activity of the β-Bi2O3 was evaluated by measuring the degradation of Rhodamine B（Rh B） under visible light irradiation. The results showed that the powders consisted of nanoflakes. The β-Bi2O3 exhibited a smaller band gap energy and larger absorbance edge than α-Bi2O3 and reported β-Bi2O3. In addition, 99.23% of the Rh B was degraded under 4 h visible light irradiation and β-Bi2O3 was a fairly stable photocatalyst under the experimental conditions.