In light of today’s problems of global warming and energy crisis, hydrogen (H2) is viewed as one of the most promising energy carriers. Natural gas reforming and gasification of coal and petroleum coke are the most convenient ways for the large-scale production of H2 but they are not environment-friendly. H2 production by electrochemical water splitting has attracted great attention because it is a simple, sustainable, and eco-friendly process. Platinum and platinum-based catalysts are considered the most efficient catalysts for hydrogen evolution reaction (HER) because they show the highest activities and lowest overpotentials, but they are high-cost materials. The most commonly used low-cost catalysts for HER include transition-metal dichalcogenides (TMDs), layered metal oxides, carbides etc. which require a tedious synthesis procedure along with costly equipment. Here, the preparation of perforated graphene through a single-step pyrolysis method from a natural waste material (dead Bougainvillea bracts) without any activating agents is presented. Further, silver nanoparticles (Ag NPs) in weight ratios of 1:5 and 1:8 are attached to it and the composite catalyst shows pronounced activity towards HER. This study provides an easy route for efficient, stable, environment-friendly, abundant, and low-cost catalyst to sustainably produce hydrogen from electrochemical water splitting.