Hollow 3D Bi2O2CO3 microspheres were synthesized at room temperature. Bi2O2CO3 exhibited higher photocatalytic activity than those prepared by hydrothermal method. Bi2S3/Bi2O2CO3 microspheres were synthesized via one-pot route at room temperature. Bi2S3/Bi2O2CO3 exhibited enhanced photoreactivity for RhB and CV degradation.