Sunlight-driven photocatalysis processes have aroused remarkable consideration to solve energy crises and environmental remediation issues simultaneously. Under this context, different efforts have been made by various research groups to enhance the photocatalytic performance of several photocatalysts. Among different factors, charge separation is one of the important features which strongly influence the photodecomposition ability of photocatalysts. In this chapter, the usage of different photocatalysts such as nanostructured metal-oxide, their heterostructures, 2D-TMDCs, plasmonic nanocomposites, and perovskite oxide with their efficient charge separation mechanism is explained briefly. This also includes the advanced approaches to engineering the different photocatalysts to tune the charge separations for enhanced photocatalytic performance. This also highlights the probable practical applications and future perspectives of advanced photocatalysts.