The development of highly effective and low-cost electrocatalysts for energy-saving hydrogen production via water splitting is still a great challenge. Herein, porous nitrogen-doped carbon nanobowls (N-CBs) have been designed and used for the controlled growth of ultrafine rhodium (Rh) nanoparticles. With the aid of interfacial bonding of Rh and N, ultrafine Rh nanoparticles with an average size of 1.4 nm have been successfully immobilized on the N-CBs. This Rh/N-CB electrocatalyst shows superior activity and high stability for the hydrogen evolution reaction (HER) and the hydrazine oxidation reaction (HzOR). More importantly, the Rh/N-CBs exhibit high activity for hydrogen production from water electrolysis, marking with a cell voltage of 0.2 V to achieve a current density of 20 mA cm-2 when they serve as cathodic electrocatalysts for the HER and anodic electrocatalysts for the HzOR in 1 M KOH with 0.5 M hydrazine. The density functional theory calculations demonstrate that a near-zero hydrogen adsorption free energy produced by the chemical bonding of Rh with the pyrrole-N doped in N-CBs is responsible for the excellent HER activity of Rh/N-CBs electrocatalysts.