In the present study, KBiO₃ is synthesized by a standard oxidation technique while LiBiO₃ is prepared by hydrothermal method. The synthesized catalysts are characterized by X-ray diffraction (XRD), Scanning ElectronMicroscopy (SEM), BET surface area analysis and Diffuse Reflectance Spectroscopy (DRS). The XRD patterns suggest that KBiO₃ crystallizes in the cubic structure while LiBiO₃ crystallizes in orthorhombic structure and both of these adopt the tunnel structure. The SEM images reveal micron size polyhedral shaped KBiO₃ particles and rod-like or prismatic shape particles for LiBiO₃. The band gap is calculated from the diffuse reflectance spectrum and is found to be 2.1 eV and 1.8 eV for KBiO₃ and LiBiO₃, respectively. The band gap and the crystal structure data suggest that these materials can be used as photocatalysts. The photocatalytic activity of KBiO₃ and LiBiO₃ are evaluated for the degradation of anionic and cationic dyes, respectively, under UV and solar radiations.