The　electrochemical　nitrogen　reduction　reaction　(eNRR)　has　emerged　as　a　promising　strategy　for　green　ammonia　synthesis.　However,　it　suffers　unsatisfactory　reaction　performance　owing　to　the　low　aqueous　solubility　of　N2　in　aqueous　solution,　the　high　dissociation　energy　of　N≡N,　and　the　unavoidable　competing　hydrogen　evolution　reaction　(HER).　Herein,　a　MIL-53(Fe)@TiO2　catalyst　is　designed　and　synthesized　for　highly　efficient　eNRR.　Relative　to　simple　MIL-53(Fe),　MIL-53(Fe)@TiO2　achieves　a　2-fold　enhancement　in　the　Faradaic　efficiency　(FE)　with　an　improved　ammonia　yield　rate　by　76.5%　at　−0.1　V　versus　reversible　hydrogen　electrode　(RHE).　After　four　cycles　of　electrocatalysis,　MIL-53(Fe)@TiO2　can　maintain　a　good　catalytic　activity,　while　MIL-53(Fe)　exhibits　a　significant　decrease　in　the　NH3　yield　rate　and　FE　by　79.8　and　82.3%,　respectively.　Benefiting　from　the　synergetic　effect　between　TiO2　and　MIL-53(Fe)　in　the　composites,　Fe3+　ions　can　be　greatly　stabilized　in　MIL-53(Fe)　during　the　eNRR　process,　which　greatly　hinders　the　catalyst　deactivation　caused　by　the　electrochemical　reduction　of　Fe3+　ions.　Further,　the　charge　transfer　ability　in　the　interface　of　composites　can　be　improved,　and　thus,　the　eNRR　activity　is　significantly　boosted.　These　findings　provide　a　promising　insight　into　the　preparation　of　efficient　composite　electrocatalysts.　©　2024　American　Chemical　Society.