Solar water splitting provides a promising path for sustainable hydrogen production and solar energy storage. In recent times, metal–organic frameworks (MOFs) have received considerable attention as promising materials for diverse solar energy conversion applications. However, their photocatalytic performance is poor and rarely explored due to rapid electron–hole recombination. Herein, we have developed a material MOF@rGO that exhibits highly enhanced visible-light photocatalytic activity. A real-time investigation reveals that a strong π–π interaction between MOF and rGO is responsible for efficient separation of electron–hole pairs, and thereby enhances the photocatalytic hydrogen production activity. Surprisingly, MOF@rGO showed ∼9.1-fold enhanced photocatalytic hydrogen production activity compared to that of pristine MOF. In addition, it is worth mentioning here that remarkable apparent quantum efficiency (0.66%) is achieved by π–π interaction mediated charge carrier separation.