The greatest challenge of our times is to identify low cost and environmentally friendly alternative energy sources to fossil fuels. From this point of view, the decarbonization of industrial chemical processes is fundamental and the use of hydrogen as an energy vector, usable by fuel cells, is strategic. It is possible to tackle the decarbonization of industrial chemical processes with the electrification of systems. The purpose of this review is to provide an overview of the latest research on the electrification of endothermic industrial chemical processes aimed at the production of H2 from methane and its use for energy production through proton exchange membrane fuel cells (PEMFC). In particular, two main electrification methods are examined, microwave heating (MW) and resistive heating (Joule), aimed at transferring heat directly on the surface of the catalyst. For cases, the catalyst formulation and reactor configuration were analyzed and compared. The key aspects of the use of H2 through PEM were also analyzed, highlighting the most used catalysts and their performance. With the information contained in this review, we want to give scientists and researchers the opportunity to compare, both in terms of reactor and energy efficiency, the different solutions proposed for the electrification of chemical processes available in the recent literature. In particular, through this review it is possible to identify the solutions that allow a possible scale-up of the electrified chemical process, imagining a distributed production of hydrogen and its consequent use with PEMs. As for PEMs, in the review it is possible to find interesting alternative solutions to platinum with the PGM (Platinum Group Metal) free-based catalysts, proposing the use of Fe or Co for PEM application.