Polypyrrole p-toluenesulfonate (PPTS) polymers were synthesized by the electrochemical technique from 0.2M pyrrole in 0:100, 1:99, 5:95, and 10:90 water/acetonitrile solutions containing 0.1M tetraethylammonium p-toluene sulfonate (TEATS) as a supporting electrolyte. Following the cyclic voltammetry measurements, the number of electrons involved in the reaction was determined to be unity. The results of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) showed that the weight loss was most rapid in the temperature range from 533 K to 768 K, and the maximum value of the reaction rate was 0.27 mg/min at 651 K. From the temperature dependence of the electrical conductivity and electron spin resonance (ESR) measurement, a small polaron hopping conduction was suggested for PPTS polymers.