Titanium　dioxide　has　recently　received　a　lot　of　attention　as　a　potential　catalyst　for　the　electrochemical　nitrogen　reduction　reaction　(NRR).　However,　the　effect　of　surface　reconstruction　of　titanium　dioxide　during　the　phase　transition　on　electrocatalysis　has　attracted　little　attention.　Here,　we　develop　a　facile　one-pot　phase-transition　engineering　strategy　to　implant　defects　in　iron-doped　titanium　dioxide.　Our　engineering　strategy　shows　advantages　including　a　simple　synthesis　process,　phase-transition　efficiency,　cost-effective　materials,　and　scalability.　The　experimental　results　and　density　functional　theory　(DFT)　calculations　demonstrate　that　surface　oxygen　vacancies　and　doping　Fe　atoms　play　crucial　roles　as　potential　electrocatalytic　sites　for　the　NRR　on　Fe-TiO2　catalysts,　which　enables　efficient　inhibition　of　the　hydrogen　evolution　reaction　(HER).　A　high　NH3　yield　of　30.9　±　0.4　μg　h-1　mgcat.-1　and　a　Faradaic　efficiency　(FE)　of　40.4　±　1.1%　at　−0.4　V　vs　reversible　hydrogen　electrode　are　obtained　for　the　NRR,　outperforming　most　Ti-based　catalysts　reported　previously.　The　formation　and　electrocatalytic　NRR　properties　of　Mn-TiO2,　Co-TiO2,　Ni-TiO2,　and　Cu-TiO2　are　also　verified.　©　2023　American　Chemical　Society.