Cs-doped alpha-Bi2O3 was synthesized via a facile hydrothermal reaction. The phase formations of the samples were investigated via X-ray powder diffraction (XRD) patterns and structural refinements. The samples present well-crystalized microplates with smooth surfaces and a thickness about 300 nm. The experiments revealed that the undoped and Cs-doped alpha-Bi2O3 microplates could crystallized in a pure monoclinic phase. The band gap of alpha-Bi2O3 could be reduced via the Cs-doping in the lattices. The photocatalytic activity on photo-degradation of methylene blue (MB) was significantly improved with the Cs-doping. The effective photocatalysis was discussed on the improved visible-light response, the enhanced dispersion in the valence band composed of hybrid orbitals of Bi6s, O2p and Cs3d, and the lowered electron-hole recombination.