Thick, 3–14 mil, free‐standing polypyrrole films incorporating a large variety of anion “dopants” were anodically deposited from aqueous electrolytes. Four‐point probe conductivity and x‐ray diffraction measurements were made and compared. Aromatic and very large amphiphilic sulfonate dopants provided the highest conductivities (up to 120 S cm−1), stabilities, mechanical properties, and apparent order. The dodecylbenzenesulfonate system was the most stable, being unaffected by even concentrated aqueous ammonia. A qualitative voltammetric technique which probes the relative order in as‐deposited thin films is introduced.