The traditional power-wasting Haber- Bosch process still dominates industrial NH3 production. Recent years witnessed the rapid development of an electrochemical N-2 reduction reaction (NRR) because of its environmentally benign and sustainable feature. Here, we demonstrate the first utilization of a Ti3C2Tx MXene nanosheet as both the precursor and conductive substrate toward the in situ hydrothermal growth of TiO2 nanoparticles. The marriage of TiO2 and Ti3C2Tx leads to a synergistically active Ti-based nanohybrid catalyst that can strengthen N 2 reduction electrocatalysis. When tested in 0.1 M HCl, such a TiO2/Ti3C2Tx hybrid is superior in catalytic performance, capable of affording a NH3 yield of 26.32 mu g mg(-1) cat. with a 8.42% Faradaic efficiency (FE) at -0.60 V versus reversible hydrogen electrode (RHE), larger than those for TiO2 and Ti3C2Tx. Notably, this nanohybrid also shows good NH3 selectivity with high electrochemical durability.