We contrast the performance of monolayer electrodes and thin porous film electrodes of highly reduced functionalized graphene to demonstrate that the introduction of electrode porosity gives rise to strong apparent electrocatalytic effects resulting in vastly improved electrode selectivity. This is despite graphene showing no intrinsic advantage over glassy carbon electrodes when used as a monolayer. The simultaneous electrooxidation of ascorbic acid, dopamine and uric acid is used as an experimental model electrolyte system. Our results suggest that a large number of reports claiming the superior surface chemistry of carbon nanomaterials as the reason for outstanding electrochemical characteristics should be revisited considering electrode morphology as a significant contributor to the observed behavior. Our experimental results are supported by numerical simulations explaining the porosity-induced electrode selectivity by the dominance of pore depletion over diffusion-limited currents.