Polypyrrole (PPy), Poly(N-methyl Pyrrole) (PMPy) and Poly(N-phenyl Pyrrole) (PPhPy) films in acetonitrile (Af and propylene carbonate (PC) have been compared focusing on their different ion and solvent transport behaviors. During the redox reaction of PPy films, cation, anion, and solvent take part in mass transport. Whereas during the redox reaction of PMPy and PPhPy films, anion and solvent transport are dominant but cation transport is negligible. In addition, solvent transport occurs in the same direction with cation transport for PPy films. On the other hand, solvent transport occurs in the opposite direction to anion transport for PMPy films, and it changes its amount and direction with the kind of the dopant anion and the solvent used at electropolymerization for PPhPy films.