The polymerization of acrolein with aniline and also with butylamine （BA） was studied in neutral, acidic and basic solution of varying pH at various temperatures and reaction times. The yields of the polymers and their molecular weights were determined, and the reaction mechanisms were discussed from analytical results. The polymerization of acrolein with benzidine (BD) and with 4.4'-methylene dianiline (MDA) was also studied by varying mole ratios of acrolein to diamines to prepare polymers of thermoplastic or thermosetting property.