<p>Heterostructures composed of MoS₂ and graphitic carbon nitride (GCN) are emerging as promising non-noble-metal electrocatalysts for the hydrogen evolution reaction (HER). Strong interfacial interactions between MoS₂ and GCN, mediated through S–N bonding moieties, are believed to promote efficient charge separation, thereby increasing electron availability for the hydrogen-reduction process. However, direct evidence of spatial charge distribution is essential to validate this mechanism and guide the rational design of efficient non-noble-metal HER catalysts. In this study, MoS₂ nanorods wrapped with GCN layers were synthesized, together with analogous composites incorporating N-doped graphene oxide (N–GO) and graphene oxide (GO) for comparison. Structural and chemical characterization was carried out using X-ray diffraction (XRD), Raman spectroscopy, Fourier-transform infrared spectroscopy (FTIR), and field-emission scanning electron microscopy (FESEM). Electrocatalytic HER performance was evaluated through linear sweep voltammetry (LSV) and Tafel analysis. The MoS₂–GCN heterostructure exhibited outstanding HER activity, comparable to that of few-layer MoS₂. Conducting atomic-force microscopy (c-AFM) mapping revealed accumulation of localized electron density at graphitic edge regions, whereas electrochemical impedance spectroscopy (EIS) measurements confirmed low charge-transfer resistance. Importantly, for the first time, c-AFM-derived I–V characteristics measured at the composite-edge regions provided direct insight into electron-donation behavior, which strongly correlated with the enhanced HER performance. These findings demonstrate that integration of MoS₂ nanorods with nitrogen-doped carbon materials represents an effective strategy for developing high-performance non-noble-metal electrocatalysts for HER applications.</p> Graphical Abstract <p></p>