<p>The intelligent use of eco-friendly natural materials to design and synthesize efficient catalysts is a significant challenge in current clean organic synthesis. Heterogeneous photocatalysis is an attractive research area in organic synthesis, which faces serious challenges such as lower efficiency and selectivity than homogeneous systems. Inspired by nature, integrating organic and inorganic photocatalysts seems to be an effective strategy to enhance photocatalytic productivity. The synergy between components assists in improving the transfer and separation of photogenerated electron-hole pairs. Vitamins are small photoactive organic molecules that involve various functional groups, which can be coordinated into inorganic materials. Hence, they are attractive bioligands for developing novel hybrid inorganic-organic structures. This review highlights photocatalysts derived from water-soluble vitamins, specifically Vitamin C and B Complex Vitamins, and their use as green photocatalysts for photo-organic transformations. It is proposed that the improved photoactivity predominantly benefits from the synergistic effects of vitamins on as-prepared nanohybrids, which facilitate efficient separation and the photogenerated electron-hole pairs and photoreaction capability of nano biocatalysts. These advantages result from tuning the band gap of vitamin-derived photocatalysts to the visible light region, morphological changes, increased active surface area, and improved surface properties.</p>