A study of the stripping voltammetry of hemispherical deposits under electrochemically irreversible conditions is presented. Experiments show a difference in the stripping voltammetry of bismuth from a single crystal Au(111) electrode where the bismuth covers the surface in relatively flat film and a boron-doped diamond (BDD) electrode where the hemispherical deposits are seen on the surface. It is shown using mathematical modeling and numerical simulation that this difference cannot be accounted for by simply considering the different distributions of bismuth on the electrode surfaces. Rather, it is concluded that the difference in voltammetry is mainly due to the morphology/orientation of the deposits formed leading to differences in the kinetics and thermodynamics of the stripping process.