Hydrogen, as a sustainable and high-efficiency fuel of the future, has prompted research into innovative photocatalytic biohybrid systems. These systems merge semiconductors with biological cells or enzymes, enabling efficient chemical synthesis, carbon dioxide reduction, and nitrogen fixation. Key steps in these systems include solar energy capture, electron transport, and energy conversion. Enhancing electron transfer speed from nanomaterials to cells is critical for optimizing performance. Covalent bond-click chemistry, such as azide-alkyne cycloaddition, is emerging as a promising strategy to improve biohybrid stability and efficiency. Notably, bacteria like Shewanella oneidensis have shown the ability to incorporate azide-modified sugars into their cell membranes, enhancing electron transfer efficiency. Carbon quantum dots, with tunable surface chemistry, have been successfully integrated into cell membranes via metabolic systems, leading to the efficient production of solar hydrogen without the need for organic carbon sources. These advancements highlight the potential of biohybrid systems in sustainable energy production and the importance of exploring novel strategies for efficient electron transfer and stability.