The paper presents the design and synthesis of nitrogen (N) and phosphorus (P) dual-doped graphene as a non-metallic catalyst for electrocatalytic hydrogen evolution reaction (HER). The authors used density functional theory (DFT) calculations to explore the effects of various dopants on the electronic properties of graphene, selecting N and P as codopants due to their contrasting charge populations. The theoretical predictions showed that the dual-doped graphene exhibited the highest HER activity compared to single-doped samples. Experimental validation confirmed that the N,P-graphene catalyst demonstrated lower overpotentials and higher exchange current densities than other investigated catalysts, with comparable performance to some traditional metallic catalysts. The catalyst also showed robust stability and applicability across a wide pH range. The synergistic coupling effect of N and P heteroatoms was quantitatively evaluated, and the results validated the predictive capability of the employed DFT model. The study highlights the potential of carbon-based materials as efficient and cost-effective alternatives to noble metals in hydrogen production.The paper presents the design and synthesis of nitrogen (N) and phosphorus (P) dual-doped graphene as a non-metallic catalyst for electrocatalytic hydrogen evolution reaction (HER). The authors used density functional theory (DFT) calculations to explore the effects of various dopants on the electronic properties of graphene, selecting N and P as codopants due to their contrasting charge populations. The theoretical predictions showed that the dual-doped graphene exhibited the highest HER activity compared to single-doped samples. Experimental validation confirmed that the N,P-graphene catalyst demonstrated lower overpotentials and higher exchange current densities than other investigated catalysts, with comparable performance to some traditional metallic catalysts. The catalyst also showed robust stability and applicability across a wide pH range. The synergistic coupling effect of N and P heteroatoms was quantitatively evaluated, and the results validated the predictive capability of the employed DFT model. The study highlights the potential of carbon-based materials as efficient and cost-effective alternatives to noble metals in hydrogen production.