Green hydrogen, produced sustainably, offers an energy solution with minimal environmental impact. For this, it is necessary to explore and exploit new renewable energy sources that respect the environment. The liquid effluents including domestic and industrial wastewaters are a promising source of hydrogen due to their abundance, accessibility, and low cost. Thus, the application of systems capable of producing hydrogen while treating wastewater is crucial for reducing greenhouse gas emissions and recovering wasted energy. Electrocoagulation (EC) offers a novel approach to hydrogen production from organic molecules in waste products, using electrodes instead of chemicals in contrast to traditional coagulation and flocculation methods. The process applies electrical current to an electrochemical reactor with effluent and electrodes, extracting hydrogen from wastewater efficiently. This study investigated the use of stainless steel (SS) and aluminum (Al) electrodes in two different anode-cathode (SS-Al, Al-SS) combinations in a batch electrocoagulation process to achieve significant COD removal and hydrogen production. The results showed that the COD removal efficiencies were 38.12% and 56.11% using SS-Al electrodes combination and Al-SS electrodes combination, respectively. The volume of gas produced was almost similar for both the two-electrode combinations when the current density was 200 A m−2 within 25 min.