The composites of the polypyrrole (PPy) and polyelectrolyte copolymers (PE) were prepared by electrochemical polymerization. The various compositions of the polyelectrolyte copolymers were used as a dopant, and were composed of copolymers of water-soluble polymers and 2-Acrylamido-2-methyl-1-propane sulfonic acid (AMPS). Thermally sensitive (N-isopropyl acrylamide, NiPAAm) and insensitive (acrylamide, AAm) polymers were used as the water-soluble polymer. The electrochemical activity and mass change during the redox process of the PPy composites were investigated by potentiodynamic voltametry and electrochemical quartz crystal microbalance (EQCM). The mass change during the redox process was mainly concerned with the cation in the electrolyte solution. When the electrochemical activity of the PPy was larger than the amount of the polyelectrolyte anion (AMPS), the insertion/expulsion of the monoanion (ClO4-) into/from the PPy composite also occurred to ionically bond with the PPy in the redox process. The PPy/P(NiPAAm/AMPS) shows a significant mass decrease with increasing the temperature compared with the PPy/P(AAm/AMPS). The transition temperature of the PPy/P(NiPAAm/AMPS) is higher in the oxidized state than in the reduced state. The transition temperature of PPy composite increases with the composition of the hydrophilic electrolyte (AMPS).