The film substructure of electrochemically prepared polypyrrole (PPy) films doped with p-toluene sulfonate has been studied using electron and optical microscopy. The solution surface of the films contained characteristic nodular features, which cap underlying cone-shaped structures. The PPy was shown to be optically active, indicating a degree of molecular anisotropy. Examination of fracture surfaces after tensile testing showed that fracture proceeded around the cones, indicating that cone boundaries are points of weakness.