AbstractAlthough it is well known that the oxidation state of polyaniline is an important characteristic, there are few reports of its influence on the development of morphology and electrical properties in fibers and films. In this work, differential scanning calorimentry is used in conjunction with measurements of temperature dependence of conductivity and thermoelectric power to elucidate the intimate relationship between structure and properties. By increasing the amount of chemical reduction of polyaniline solutions, films are prepared which exhibit a thermal transition between 300 and 385 °C, indicative of melting. Increasing the chemical reduction also increases the conductivity of iodine doped films. The most reduced film exhibited a semiconductor transport mechanism, while the other films could be modeled with a quasi-one dimensional variable range hopping mechanism. The temperature dependence of conductivity also showed increasing order for increasing reduction, consistent with the DSC results.