Noble metals (Pt) and metal oxides (IrC and RuO) are heavily utilized as benchmark electrocatalysts for alkaline water splitting; however, these materials possess several drawbacks including high cost, poor selectivity and stability, and high environmental impact. To address these issues, we synthesized a novel metal-free conducting polypyrrole-polythiophene (Ppy-Ptp) copolymer and a separate Ppy electrode material for water-splitting applications. The Ppy-Ptp and Ppy electrocatalysts exhibited remarkable activity in the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively. The optimal Ppy-Ptp (1:3) formulation, when deposited on a conductive nickel foam (NF) substrate, exhibited an exceptional OER performance with a low overpotential of approximately 250 mV at 20 mAcm, thereby outperforming the benchmark IrC/NF electrocatalyst (290 mV, 20 mAcm). Additionally, a similarly prepared Ppy/NF electrocatalyst exhibited an extraordinary HER performance with an overpotential of approximately 72 mV at 10 mA cm. Furthermore, an alkaline anion-exchange membrane (AEM) electrolyzer incorporating Ppy-Ptp (1:3) and Ppy as the anode and cathode materials, respectively, displayed operating potentials of 1.55, 1.70, and 1.78 V at 10, 50, and 100 mA cm, which are lower than those observed in previously reported electrolyzers. This electrolyzer also exhibited considerable operational endurance over 50 h at 50 mA cm, over which a negligible decay of 0.02 V was observed. The novel polymer-based metal-free catalysts presented herein therefore exhibit considerable potential as alternative electrocatalytic materials for sustainable industrial-scale H synthesis.