We herein achieved a novel indium-tin oxide (ITO) bipolar electrode (BPE) based sensing system by the introduction of nanoporous ITO on the cathode. The implementation of the nanoporous ITO layer in the BPE greatly boosted the ECL signal compared to the planar ITO BPE, enabling efficient detection of H₂O₂ even under mild operating voltage. The calibration curves of ECLs in H₂O₂ sensing with BPEs of various nanopore thicknesses exhibited enhancement of LODs and sensitivities with a thicker nanoporous ITO layer. We speculate that the morphology of the nanopores led to confinement of the analytes, increasing the interaction with the electrode surface, resulting in amplified ECL signals. We believe that the nanoporous BPEs are adequately suited for the extended application as a compartment in portable, in situ sensing systems, due to their low power requirements and ease of detection through the naked eye.