The present work demonstrates an isothermal reversible variation of magnetization in nanoporous Pd67Ni33 alloy during continuous charging and discharging of the alloy electrode in 1-M KOH solution. A custom-built electrochemical cell, containing the sample as working electrode performed the in situ charging experiments inside an extraction magnetometer at a constant applied magnetic field. The metal–electrolyte response was examined by varying the electrode potential, which apart from polarizing nanoporous structure, may also lead to electrodissociation of the electrolyte medium, being aqueous in nature. The result therefore analyzed hydrogenation as the key parameter for the observed reversible magnetization in the transition metal alloy at room temperature. In addition, electrochemical reactivity due to surface oxidation at the positive potential has been discussed, considering that a change in the band structure is also possible at the negative potential regime due to hydrogenation through cyclic voltammetry study.