An electrochemical nitrogen reduction reaction (NRR) under mild conditions offers a promising alternative to the traditional Haber-Bosch process in converting abundant nitrogen (N₂) to high value-added ammonia (NH₃). In this work, iron phthalocyanine (FePc) was homogeneously immobilized on pyridine-functionalized carbon nanotubes to form a well-tuned electrocatalyst with an FeN5 active center (FePc-Py-CNT). Synchrotron X-ray absorption and Fourier transform infrared spectroscopy proved the presence of an Fe-N coordination bond between FePc and surface-bound pyridine. The resulting hybrid exhibited notably enhanced electrocatalytic NRR performance compared to FePc immobilized on CNTs based on pi-pi stacking interactions (FePc-CNT), resulting in doubled NH3 yield (21.7 mu g 1 h mg_cat^-1h^-1) and Faradaic efficiency (22.2%). Theoretical calculations revealed that the axial coordination on FePc resulted in partial electron transfer from iron to pyridine, which efficiently suppresses the adsorption of H⁺ and improves the chemisorption of N₂ at Fe sites. Meanwhile, the interfacial electron transfer was facilitated by pyridine as an electron transfer relay between FePc and CNTs. This work provides a unique strategy for the design of highly efficient NRR electrocatalysts at the molecular level.