Development of free metal or non-noble-metal catalysts for electrode materials with both excellent activity and high stability is essential for hydrogen production. In this work, nitrogen rich polybenzimidazole (PBI) networks  were  synthesized  through  a  one-step  polycondensation  of  1,2,4,5-tetraaminobenzene  with 4,4 0 ,4 00 -((1,3,5-triazine-2,4,6-triyl)tris(azanediyl))tribenzoic  acid.  Then,  organic/inorganic  nanohybrids  of PBI with amorphous MoS 2 nanoplates (PBI – MoS 2 ) were prepared. The structural characterization and morphological   of   these   novel   hybrids   were   studies   using   FT-IR, H   NMR,   elemental   analysis, thermogravimetry, transmission electron microscopy, fi eld-emission scanning electron microscopy and X-ray di ff raction techniques. Electrochemical studies revealed the onset potential of only (  160 mV vs. RHE) with a small Tafel slope of 50.6 mV dec  1 for hydrogen generation reaction in 0.5 mol L 1 H 2 SO 4 . Stability tests through long term potential cycles con fi rm the excellent durability of PBI – MoS 2 in acid media. The outstanding hydrogen generation activity is derived from the electronic penetration e ff ect and H + absorption of pyridinic-N and/or pyrrolic-N as active sites at per repeat of the PBI matrix. It is worth  noting that  pure  PBI  and  PBI – MoS 2 hybrids, for  the fi rst  time,  were  used  as  both  anode  and cathode in two-electrode system open up new possibilities for exploring overall hydrogen generation technology catalysts in acidic electrolyte. This development o ff ers an attractive electrocatalyst for largescale hydrogen generation.