Herein, we constructed amorphous ReS₂ nanosheets anchored on TiO₂ nanowires by delicately forming Ti–O–Re bonds, which exhibited considerable average ammonia yield and faradaic efficiency as high as 5.3 μg h⁻¹ cm⁻²_cat. and 49.8% at an applied potential of −0.2 V (vs. RHE) in 0.1 M Na₂SO₄. The high NRR performance could be attributed to the amorphous feature of the ReS₂ nanosheets, the rich oxygen vacancies in the TiO₂ nanowires and their semiconducting feature, which not only facilitate the sufficient exposure of active sites but also efficiently boost the faradaic efficiency due to the good regulation of surface proton or electron accessibility.