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The present study aims to examine and evaluate the concept of H2S decomposition to H2 production in (H2)-conducting electrochemical reactors. In such a complex process, one of the major issues raised is the optimal selection of materials for the electrochemical cell. Specifically, the anode electrode should exhibit high catalytic activity and electronic conductivity, in order to make the process efficient. In this context, and before the electrochemical tests, a number of transition metal catalysts supported on CeO2 were prepared using the wet impregnation method and tested for their performance regarding the activity/stability of the H2S decomposition reaction, in the absence and presence of H2O. The experimental results are accompanied by the corresponding thermodynamic calculations, at various reaction conditions. The physico-chemical characteristics of the employed catalysts were determined using the BET, XRD, SEM and elemental analysis methods. The experimental results showed that the catalysts 20% wt. Co/CeO2 and 30% wt. Co/CeO2 exhibit high H2S conversions, in the absence and presence of H2O respectively, comparable to conversions indicated by thermodynamics and with remarkable stability, which is attributed to the in-situ sulfation of catalysts’ active components during their exposure at the feedstock mixture