Abstract Scanning electrochemical microscopy (SECM) enables the study of mass transport in porous substrates with microscale spatial resolution, which is profoundly influenced by the substrate's architecture. Here, a 3D SECM modeling was used to compare the impact of substrate geometry on transport in three porous structures: a superposition (SP) and two high fidelity (HF-1 and HF-2) models. It was found that the steady-state current decreases with an increase in the geometric complexity from SP to HF-1 to HF-2, indicating the presence of more tortuous paths in HF-2. Despite having the same porosity and thickness values, the disparity between the SP and the two HF substrates shows the effect of microporous geometry. Our findings also demonstrated the deviation of all three substrates from Bruggeman's predictions, which highlights the significance of modeling to rationalize the transport properties in commercial battery electrodes.