Electrochemical water splitting driven by renewable energy sources is considered to be a promising carbon-free pathway for the production of the “green” fuel hydrogen. Efforts for decarbonization are recurrent, so the use of electrochemical technology powered by renewable sources, such as photovoltaic cells (PV), wind turbines, among other alternatives, have increasingly attracted the attention of the scientific community. Despite the promises of such an approach, the process economics are not yet favorable. Faced with this scenario, propositions arise such as the integration of processes. The use of membrane divided electrochemical reactors is a well-known technology in hydrogen production (at the cathodic compartment). The proposal is the simultaneous production of green hydrogen with anodic reactions. Then, on the one hand, the supply of electrical energy to promote anodic reactions in the production of strong oxidants is an alternative to be considered for the parallel production of hydrogen, reducing energy consumption and costs; Being an eco-friendly sustainable process, if the electricity is produced by PV cells. On the other hand, the use of a boron-doped diamond electrode, in the anodic electrolytic compartment, can be considered a promising alternative, because the wastewater treatment, disinfection of water or electrosynthesis of oxidants can be attained. Thus, this work proposed the production of sulfate-based oxidizing species in the anode compartment with the simultaneous production of green H2 in the cathode compartment. Results clearly have demonstrated that higher production efficiencies, from 0.5 to 2.0 mM, of sulfate-based oxidizing species can be obtained depending on applied current densities, producing in parallel, from 0.2 to 0.8 L of pure hydrogen in 120 min. Application ex-situ of electrogenerated persulfate stored at lower temperatures has greater applicability than when stored at room temperature. The transition from “on-grid” to “off-grid” technology has some advantages such as cost reduction, ease of logistics and greater process portability and reproducibility. Sulfate-based oxidizing species solutions can be used as an off-grid technology to degrade pollutants, thus, increasing the high-added value of the technology.