Electrochemical nitrogen reduction reaction (NRR) is considered as one of the most promising methods for NH 3 synthesis under room temperature and ambient pressure. A grand challenge of NRR is the development of efficient electrocatalysts, for which the delicate nanostructuring of catalysts plays an important role. Herein, a series of Fedoped Cu 2−x S quantum dots (QDs) are synthesized with multiple active sites and interface engineering, in which the double-phase heterostructure plays a key role for boosting NRR activity. The yield of NH 3 was obviously improved with the increase of Fe content from 0 to 3% but started to decrease with Fe from 3 to 9%. The optimized Fe 3% −Cu 2−x S QDs show an outstanding NH 3 yield of 26.4 μg h −1 mg −1 cat at −0.7 V (vs the reversible hydrogen electrode), which is 5 times higher than that of Cu 2−x S QDs. More importantly, we observed that the highest NRR activity in Fe 3% −Cu 2−x S QDs was ascribed to the formation of an inherent double-phase heterostructure of Cu 2−x S/Cu 5 FeS 4 , whereas the complete conversion to single-phase Cu 5 FeS 4 with increased Fe doping (9%) resulted in the activity decrease. Further, N 2 temperature-programmed desorption and electrochemical impedance spectra characterizations confirm the stronger chemical adsorption of N 2 and faster charge transfer in the Cu 2−x S/Cu 5 FeS 4 QDs. A plausible mechanism was proposed for the double-phase Cu 2−x S/Cu 5 FeS 4 heterostructure, where the interface provides efficient charge transfer and more active sites of Cu, Fe, and S for the synergetic adsorption and activation of N 2 . Our work provides a simple strategy for the design of NRR electrocatalysts, which may also bring new inspiration for the preparation of the inherent double-phase heterostructure within other doped QDs.