Photo nanocatalyst have shown promise in a variety of fields, including biohydrogen production where their catalytic efficiency is related to size, surface-to-volume ratio, and increasing the number of atoms on the surface. They can harvest solar light to create electron-hole pairs which is the key mechanism to define its catalytic efficiency, thus requiring suitable excitation wavelength, band energy, and crystal imperfections. In this review, a discussion on the role of photo nanocatalysts to catalyze biohydrogen production has been carried out. Photo nanocatalysts feature a large bandgap, and high defect concentration, thus having the ability to be tuned for their characteristics. Customization of the photo nanocatalyst has been addressed. Mechanism of the photo nanocatalysts in catalyzing biohydrogen has been discussed. Limiting factors of photo nanocatalysts were highlighted and several recommendations have been made to enhance the effective utilization of these photo nanocatalysts to enhance photo-fermentative biohydrogen production from biomass wastes.