Cellulose and hemicellulose are the main constituents of lignocellulosic biomass. Chemical derivatization of lignocellulosic biomass leads to a range of C5 and C6 organic compounds. These C5 and C6 compounds are valuable precursors (or fine chemicals) for developing sustainable chemical processes. Therefore, depolymerization of cellulose and hemicellulose is essential, leading to the development of various materials that have applications in biomaterial industries. However, most depolymerized processes for cellulose have limited success because of its structural quality: crystallinity, high hydrogen-bond networking, and mild solubility in organic and water. As a result, various chemical treatments, acidic (mineral or solid acids) and photocatalysis, have developed. One of the significant shortcomings of acidic treatment is that the requirement for high temperatures increases the commercial end cost (energy) and hampers product selectivity. For example, a catalyst with prolonged exposure to high temperatures damages the catalyst surface over time; therefore, it cannot be used for iterative cycles. Photocatalysts provide ample application to overcome such flaws as they do not require high temperatures to perform efficient catalysis. Various photocatalysts have shown efficient cellulosic biomass conversion into its C6 and C5 hydrocarbons and the production of hydrogen (as a green energy component). For example, TiO2-based photocatalysts are the most studied for biomass valorization. Herein, we discussed the feasibility of a photocatalyst with application to cellulosic biomass hydrolysis.