Abstract: Rational preparation of cost-effective and efficient metal-free carbon-based catalysts for hydrogen evolution reaction (HER) is of great significance for boosting the flourishing of clean hydrogen production from alkaline water electrolysis. Delicate regulation of the electronic structure via heteroatom doping has proven to be efficient for enhancing intrinsic catalytic activity. Nevertheless, both the structural characteristics and the underlying mechanism lack comprehensive investigation and remain greatly obscure especially for dual atoms doping, impeding the practical use of metal-free carbon-based HER catalysts. Herein, phosphorus/nitrogen co-doped hollow carbon nanospheres (HCNs) were successfully synthesized via the copolymerization of pyrrole and aniline at Triton X-100 micelle-interface, followed by doping with phytic acid and carbonization. The unique pore structure and defect frameworks of HCNs promote the exposure of numerous active sites. Crucially, the combined coupling effect of graphitized nitrogen (N―Q) and phosphorus-carbon (P―C) bonds modulates the local electronic structure of adjacent C atoms and facilitates electron transfer. Therefore, the HCN carbonized at 1100 °C exhibited superior alkaline HER activity and outstanding stability (70 h@10 mA cm⁻²), owing to the larger proportion of N―Q and P―C bonds.