Electrochemical nitrogen fixation techniques have emerged as a promisingly sustainable approach to face the challenge associated with nitrogen activation of ammonia synthesis by the Haber–Bosch process under ambient conditions. Herein, the performance of electrocatalytic nitrogen reduction for the production of α‐Fe2O3 nanospindles coated with mesoporous TiO2 with different crystallinity [denoted as α‐Fe2O3@mTiO2‐X (X=300, 400, and 500 °C)] were investigated. The as‐prepared α‐Fe2O3@mTiO2‐400 composite exhibits a large NH3 yield (27.2 μg h−1 mgcat.−1) at −0. 5 V vs. the reversible hydrogen electrode and a high Faradaic efficiency (13.3 %) in 0.1 m Na2SO4, with excellent electrochemical durability. This work presents a novel avenue for the rational design of efficient unique hetero‐phase nanocatalysts toward sustainable electrocatalytic N2 fixation.