The synthesis, structure, optical and photocatalytic studies of a family of compounds with the general formula, BiMXO 5 ; M = Mg, Cd, Ni, Co, Pb, Ca and X = V, P is presented. The compounds were prepared by regular solid-state reaction of constituents in the temperature range of 720-810°C for 24 h. The compounds were characterized by powder X-ray diffraction (PXRD) methods. The Rietveld refinement of the PXRD patterns have been carried out to establish the structure. The optical absorption spectra along with the colors in daylight have been explained employing the allowed d-d transition. In addition, the observed colors of some of the V 5 + containing compounds were explained using metal-to-metal charge transfer (MMCT) from the partially filled transition-metal 3d orbitals to the empty 3d orbitals of V 5 + ions. The near IR (NIR) reflectivity studies indicate that many compounds exhibit good NIR reflectivity, suggesting that these compounds can be employed as 'cool pigments'. The experimentally determined band gaps of the prepared compounds were found to be suitable to exploit them for visible light activated photocatalysis. Photocatalytic CÀ C bond cleavage of alkenes and aerobic oxidation of alcohols were investigated employing visible light, which gave good yields and selectivity. The present study clearly demonstrated the versatility of the Paganoite family of compounds (BiMXO 5) towards new colored inorganic materials, visible-light photocatalysts and 'cool pigments'.