The Bi3+-containing semiconductors have been widely reported as potential photocatalyst candidates for water-splitting and environmental pollution problems. This work reported a new kind Bi-heterojunction of LiBiO2/Bi2O3, which was synthesized by the facile hydrothermal reactions. The XRD (X-Ray powder diffraction) measurement was applied to investigate the phase formations. The composite crystals developed in the well crystallized ultrathin nanosheets with the thickness about 320 nm. The UV-visible absorption indicated that LiBiO2/Bi2O3 heterojunction has a similar optical absorption edge to that of LiBiO2 (2.04 eV). This confirms the heterojunction has the actively optical abilities in visible wavelength region. The photocatalytic activities were tested by photo-degradation effects of rhodamine B (RhB) dye and colorless phenol solutions under the visible light irradiation. The experiments suggested that the photocatalysis activities could be greatly improved via coupling Bi2O3 in LiBiO2/Bi2O3 heterojunctions. The migration of light-induced charge-carriers adopts a typical direct Z-scheme in LiBiO2 and LiBiO2/Bi2O3 heterojunctions. (C) 2019 Elsevier B.V. All rights reserved.