Using β, β' dimethylpyrrole polymers to reduce the structural disorder it has been possible to interpret the results of electron diffraction data and to propose an idealized structure for neutral polypyrrole. XPS data have been used to define some of the deviations from this ideal structure that are seen in actual films and the origin of some of these defects is related to the mechanism of polymerization. The planarity of the chain structure is shown to be important for high conductivity in pyrrole polymers which appears to involve spinless carriers perhaps associated with bipolarons.