Appropriately dealing with real surface area evaluation in organic electrocatalysis implies working mostly in organic media, and, above all, adopting molecular probes. Their selection is not straightforward, implying preliminary knowledge of the structural and mechanistic effects possibly modulating the probe molecule’s perspective of the electrode surface. Taking the electrocatalytic reduction of organic bromides on polycrystalline silver as a model process, we propose a stepwise approach to the evaluation of catalytic active surface areas, relative to a non-catalytic reference one, particularly focusing on the modulating effects of the bulkiness and reactivity of the probe molecules.