Hydrogen production from organic hydrides represents a promising strategy for the development of safe and sustainable technologies for H2 storage and transportation. Nonetheless, the majority of existing procedures rely on noble metal catalysts and emit greenhouse gases such as CO2/CO. Herein, we demonstrated an alternative N-doped carbon (CN) catalyst for highly efficient and robust H2 production from an aqueous solution of formaldehyde (HCHO). Importantly, this process generated formic acid as a valuable byproduct instead of CO2/CO, enabling a clean H2 generation process with 100% atom economy. Mechanism investigations revealed that the pyrrolic N in the CN catalysts played a critical role in promoting H2 generation via enhancing the transformation of O2 to generate •OO- free radicals. Consequently, the optimized CN catalysts achieved a remarkable H2 generation rate of 13.6 mmol g-1 h-1 at 30 °C. This finding is anticipated to facilitate the development of liquid H2 storage and its large-scale utilization.