<p>In this study, N-graphyne/α-FeOOH composites are fabricated through a one-pot hydrothermal process. In the resulting structure, the wrinkled layers of N-graphyne envelop the α-FeOOH nanorods, forming intimate heterostructures with strong interfacial contact. The photo-Fenton reaction parameters are systematically explored including light irradiation, catalyst and H₂O₂ dosage, and solution pH. A 1.65-fold enlargement toward tetracycline degradation is achieved in the photo-Fenton reaction using N-graphyne/α-FeOOH in comparison with α-FeOOH alone. The catalytic stability of the composites in the photo-Fenton reaction is verified through recycling degradation tests and X-ray diffraction analysis. The incorporation of N-graphyne enhances photo-response and facilitates charge carrier separation, as systematically demonstrated by photocurrent measurements, turnover frequency, Mott–Schottky plots, Tafel curves, electrochemical impedance spectroscopy, photoluminescence spectroscopy, and UV–Vis diffuse absorption spectroscopy. The increased photogenerated charges boost the photo-Fenton process both by directly generating radicals and by sustaining the Fe³⁺/Fe²⁺ redox cycle for H₂O₂ activation into OH^• radicals. This study demonstrates for the first time the feasibility of N-graphyne in enhancing the photo-Fenton activity of α-FeOOH, which develops a strategy that can be extended to optimize other photo-Fenton, photo-Fenton-like, Fenton, and even photocatalytic material systems.</p> Graphical Abstract <p>A novel N-graphyne/α-FeOOH catalyst is firstly constructed and its enhanced photo-Fenton catalytic performance/mechanism towards tetracycline degradation is systematically investigated. </p> <p></p>