<p>Glassy carbon electrodes were modified with a CeO₂ film and Pt nanoparticles (Pt-CeO₂) for electrocatalysis. Interestingly, the oxidation of benzyl alcohol was significantly enhanced when Pt-CeO₂ films were prepared by the simultaneous electrodeposition of the two materials, indicating a significant synergistic electrocatalytic activity. Subsequently, bipolar electrochemistry was employed to prepare Pt-CeO₂ gradient films. Scanning electrochemical microscopy (SECM) was employed for studying local electrochemical properties at liquid/solid interfaces. SECM allowed mapping the local electrochemical performance of the Pt-CeO₂ gradient films for benzyl alcohol oxidation, showing that the reaction rate is proportional to the local Pt-CeO₂ surface coverage. Therefore, Pt-CeO₂ deposits with different densities along the bipolar electrode offer tunable catalytic performances for benzyl alcohol oxidation. This allows identifying in a fast and straightforward way the optimal conditions for electrocatalytic processes in a more general sense because the approach, illustrated here with one specific reaction, can be easily generalized to other catalytically active surfaces.</p> Graphical Abstract <p></p>