The transition metal nitrides (TMNs) with nanoporous structure have shown great promise as potential electrocatalysts for the hydrogen evolution reaction (HER). Herein, self-organized nanoporous Nb2N was first successfully synthesized through the anodization of niobium in mixed oxalic acid/HF electrolyte, followed by a simple annealing treatment in the ammonia atmosphere. Due to the highly ordered nanoporous structure with abundant active sites and the enhanced electrical conductivity, the Nb2N exhibits a high catalytic current (326.3mAcm−2) and low onset potential (96.3mV), which is almost 3.9 times and 4.2 times better than that of Nb2O5, respectively. Meanwhile, the Nb2N also presents low Tafel slope (92mVdec−1), and excellent cycling durability. More importantly, this study will provide more opportunities for designing and fabricating niobium compounds as an innovative HER catalysts.