Electrodialytic technologies are defined as treatment processes that promote the removal/recovery of substances in a matrix, based on the application of low-level current intensities. Additionally, along these processes hydrogen is self-generated, allowing them to operationally produce clean energy. This energy carrier is produced due to electrolysis reactions occurring at the cathode end of the electrodialytic reactor, when using inert electrodes. Herein, hydrogen production during the electrodialytic treatment of sewage sludge and mining residues suspensions (coupled with effluent or sewage sludge), at 50 and 100 mA, was assessed. During the electrodialytic treatment of sewage sludge, hydrogen purity production achieved 33%. When effluent or sewage sludge were used as enhancements in mining residues suspensions, hydrogen purity reached 71% and 34%, respectively. Furthermore, a proton-exchange membrane fuel cell was connected to the cathode compartment of the electrodialytic reactor. The electrical energy generated from self-hydrogen produced at 100 mA achieved ≈1 V in all performed experiments. Simultaneously, critical raw materials extraction, namely phosphorus and tungsten, was evaluated. When the process was applied to mining residue suspensions combined with sewage sludge, the highest extraction ratio of phosphorus (71%) and tungsten (62%) was observed.