A structural and micro-pore analysis of a series of heat treated electrolytic manganese dioxide (EMD) samples has been conducted. In terms of crystal structure, the original EMD with γ-MnO2 structure (orthorhombic unit cell) was found to progressively convert to β-MnO2 (tetragonal unit cell) at elevated temperatures. The structural transition was kinetically limited, with the higher temperatures leading to a greater degree of transformation. The orthorhombic γ-MnO2 unit cell was found to contract along the a and b axes, while along the c axis an expansion was observed only at the highest heat treatment temperatures. These changes occur as a result of manganese ion diffusion leading to the formation of a denser, more defect free material. The porosity of these heat treated EMD samples was also examined by N2 gas adsorption combined with various interpretive techniques such as the Kelvin equation, MP method, Dubinin–Radushkevich method, Dubinin–Astakhov method and a more modern density functional theory based approach. Despite shortcomings associated with certain techniques, all clearly indicated that the EMD micro-pore volume decreased and the meso- and macro-pore volume increased as the heat treatment temperature was increased. This was justified as a result of manganese ion movement during the structural rearrangement causing the small pores to be progressively sintered shut, while the larger pores were formed as a result of stress-induced cracking in the denser final product.