To harvest solar energy efficiently, a series of Zn/Bi layered double hydroxide (LDH) photocatalysts with different molar ratios of Zn/Bi (2 : 1, 3 : 1, 4 : 1) has been synthesized by a coprecipitation method at constant pH. All the Bi doped LDH samples displayed hydrotalcite-like structure with interlayer carbonate, in which crystallinity decreases as the bismuth content increases. The Zn/Bi (4 : 1) LDH with a small amount of bismuth in the brucite layer and possessing high crystallinity was further modified hydrothermally by intercalating decavanadate and it showed high photochemical stability and photocatalytic activity for the degradation of different organic pollutants for practical applications under solar light irradiation. The structural integrity of the materials has been successfully characterized by studying their structural, morphological, electronic and optical properties by various physico-chemical techniques. The present study provided an insight into oxo-bridged MMCT of the LDH and established that the Zn(II)-O-Bi(III) units resulted in the generation of superoxide radicals which is clearly observed by the EPR technique. The ˙OH radicals formed during photocatalysis were revealed by means of the terephthalic acid fluorescence probe method. The photoelectrochemical measurement confirmed that the intercalated vanadate anion was crucial to obtain an optimal synergistic effect for the degradation of organic pollutants. The prolonged lifetime of photogenerated charges and improved charge transfer capability were confirmed by time-resolved fluorescence emission spectra. Furthermore, a detailed mechanism for the enhanced photocatalytic activity was discussed.