Platinum usually offers the most effective active center for hydrogen evolution reaction (HER), because of the optimal trade‐off between the adsorption and desorption of hydrogeN atoms (H*) on Pt atoms. Herein, we report an unusual result regarding the active center of a HER catalyst, which was synthesized by electrodepositing traces of Pt nanoparticles (NPs) into a porous nitrogen‐rich dodecahedron matrix derived from zeolitic imidazolate framework ZIF‐8. With an ultra‐low Pt loading of 2.76 μg cm−2, the N‐Pt‐bonded catalyst can produce a current density of 117 mA cm−2 for the HER in 1.0 m H2SO4 at an overpotential of 50 mV, whereas the commercial Pt/C (300 μg cm−2 Pt) can only reach 50 mA cm−2 under the same conditions. Cyclic voltammetry demonstrates that both the H* adsorption and the Pt oxidation are not allowed to occur on this catalyst, due to a full surface coverage of the trace Pt NPs by imidazole. The results from the specially designed experiments indicate that the imidazole N atoms may act as proton anchor‐sites for the HER due to their electron donor nature. Density functional theory calculations also support a catalytic HER mechanism centered at the Pt‐supported N active center, which needs a Gibbs free energy of H* absorption (ΔGH*) significantly smaller than the absolute value of ΔGH* on the Pt(111) surface. We hope that the results of this study will encourage the research on novel N‐centered catalysts for the HER. Role reversal: Imidazole N atoms prove to be the real active center of a highly efficient ZIF‐8‐derived electrocatalyst for hydrogen evolution reaction (HER), even in the presence of trace Pt (a well‐known active center). Neither H* adsorption nor Pt oxidation can occur on the nonexposed Pt surface (fully covered by imidazole).