Bimetallic compounds such as hydrotalcite-type layered double hydroxides (LDHs) are promising electrocatalysts owing to their unique electronic structures. However, their abilities toward nitrogen adsorption and reduction are undermined since the surface-mantled, electronegative –OH groups hinder the charge transfer between transition metal atoms and nitrogen molecules. Herein, a smart interfacing strategy is proposed to construct a coupled heterointerface between LDH and 2D g-C₃N₄, which is proven by density functional theory (DFT) investigations to be favorable for nitrogen adsorption and ammonia desorption compared with neat LDH surface. The interfaced LDH and g-C₃N₄ is further hybridized with a self-standing TiO₂ nanofibrous membrane (NM) to maximize the interfacial effect owing to its high porosity and large surface area. Profited from the synergistic superiorities of the three components, the LDH@C₃N₄@TiO₂ NM delivers superior ammonia yield (2.07 × 10⁻⁹ mol s⁻¹ cm⁻²) and Faradaic efficiency (25.3%), making it a high-efficiency, noble-metal-free catalyst system toward electrocatalytic nitrogen reduction.