The unique nanosheet-based flower-like BiOCl1−xBrx (x=0–1) hierarchical solid solutions have been prepared by the reaction of Bi2O3 and KCl/KBr in mixed solution of glacial acetic acid (HAc) and H2O in dozens of minutes under ambient conditions. During the preparation process, the intermediate bismuth oxide acetate (CH3COOBiO) plays a key role in the formation of BiOCl1−xBrx solid solutions in such a short time. The as-prepared hierarchical BiOCl1−xBrx solid solutions possess high specific surface areas and modified band structures, which exhibit enhanced photocatalytic activity for Rhodamine B (RhB) degradation in comparison with pure BiOCl and BiOBr under visible light irradiation, with the activity reaching the maximum at x=0.5. The photodegradation efficiency of the BiOCl0.5Br0.5 solid solution is twice and 12times higher than P25 TiO2 under UV and visible light irradiation, respectively.