A series of copolymers were prepared by an oxidative polymerization of pyrrole (PY) and 2-ethylaniline (EA) in HCl. The polymerization process was followed by tracking open-circuit potential and temperature of the reaction solutions. The fine particles of the PY/EA copolymers obtained in situ were further N-nitrosated for the first time in order to improve their solubility. The size, structure, and properties of the fine particles and their N-nitroso products were systematically characterized by laser particle size analyzer, MR, UV-vis, GPC, solution casting, and TG techniques. It is found that both the open-circuit potential and temperature of the solutions exhibit a maximum during the copolymerization, while the particle size of the copolymers will decrease monotonically with prolongating polymerization time or doping. Both the polymerization yield and molecular weight of the copolymers exhibit a minimum with PY/EA ratio, indicating a mutual retarding effect between the PY and EA monomers. The top potential and top temperature of the copolymerization as well as the particle size and its distribution, solubility, film-forming ability, electroconductivity, and thermostability of the copolymers all depend significantly on the PY/EA ratio. The PY/EA copolymers have good solubility in the solvents with the solubility parameter from 23 to 27 J(1/2)/2/cm(3/2), dielectric constant greater than 12 and polarity index from 6.4 to 7.4 and their solubility becomes further better with increasing EA content. The N-nitrosation of copolymers can also improve their solubility in polar solvents furthermore. The copolymers with PY content of less than 30 mol% in NMP and THF exhibit good thin-film formability. The copolymer films become smoother and tougher with increasing EA content and by N-nitrosation. With increasing PY content, the decomposition temperature, maximum decomposition rate, char yield at 500degreesC, and activation energy all decrease but decomposition order increases. The temperature at the maximum weight-loss rate of the copolymers has a maximum at the PY/EA molar ratio of 30/70. These results suggest that the polymer obtained is a real copolymer containing two comonomer units. (C) 2003 Elsevier Ltd. All rights reserved.