Compared with the traditional Haber Bosch process, green and pollution-free electrocatalytic nitrogen reduction (NRR) has received considerable attention in the electrocatalysis field in the last decade. To address the issue of its low reactivity as well as the existence of competitive reactions, efficient electrocatalysts are particularly important. In this paper, NiO nanomaterials were synthesized by a simple water bath reaction. The effect of different calcination temperatures on the structure of NiO catalyst and its catalytic activity was studied. Uniform NiO-600 nanoparticles (56 ± 9.3 nm) obtained at 600 ℃ showed the best electrocatalytic NRR activity with an NH3 yield of 12 μg h− 1 mg− 1 and a Faraday efficiency of 5.5% at -0.5V (vs.RHE). The small particle size of the nanoparticles provided more active sites and the oxygen-rich vacancies facilitated the adsorption and activation of N2, which improved the catalytic activity of NiO-600. This study highlights the need for calcination temperature regulation and the huge impact on catalyst structure.