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An H₂O₂ electrochemiluminescence (ECL) sensor with a very low detection limit has been developed using a hybrid of polypyrrole-dodesylbenzen sulfate-cerium oxide nanocomposite (PPy-DBS-CeO₂) on a Pt electrode. The incorporation of the CeO₂ nanoparticles in the polymeric matrix of the composite enhanced the ECL signal. Under optimal conditions, the signal and the logarithm of H₂O₂ concentration showed a linear relationship from 5.0 × 10⁻¹⁶ to 5.0 × 10⁻⁵ M (R² = 0.9922) and a very low detection limit of 1.2 × 10⁻¹⁶ M was observed. The sensor revealed good reproducibility and stability and was found applicable to the detection of H₂O₂ in water and milk samples.