This paper reports for the first time a computational analysis of the redox properties of graphene‐supported Ru‐porphyrins as potential catalytic materials for electrochemical CO2 reduction. Density functional theory reveals that such catalytic ensembles can efficiently activate both CO2 and CH4 molecules indicating their generic utility as C1‐functionalization catalysts. The charge transfer from the graphene surface to the catalytic Ru centers influences the thermodynamic stability of the key reaction intermediates and therefore determines the selectivity of the electrochemical process. The electrochemical reduction of CO2 can yield CO or methane, depending on the applied potential and reaction conditions. Calculations also identified alternative paths towards methanol and formic acid.