The positive active material of lead‐acid cells under deep‐discharge cycling conditions was studied. Morphological transformation and changes in surface area, density, pore‐size distribution, and composition were recorded. The relationship of these parameters to discharge capacity and ultimate failure are discussed. It was found that pores can be classified in two categories, namely, macropores with diameters larger than 0.5 μm and micropores with smaller diameters. Macropores are responsible for mass transport to and from the reaction surface provided by the micropores. In order to sustain high capacity discharge performance, an optimum structure of active material must contain both kinds of pores appropriately distributed.