Polymerizations of acrolein with phenols and acrolein with amines, and the characteristics of those polymers were investigated. The polymers of acrolein with phenols, e.g., phenol, cresol and hydroquinone were prepared when the reactions were carried out at 50-120 ℃, for 3-8 hrs. Under strongly acidic conditions, polymerization of acrolein with aniline at 25 ℃ for 30-60 minutes resulted in thermoplastic polymer of low molecular weight, and those of acrolein with benzidine and 4,4'-methylene dianiline at 0-20 ℃ for 30-60 minutes also resulted in brown crosslinked polymers. The characteristics, such as electrical insulating properties, thermostabilities, adhesivities and mechanical properties of those polymers were determined. Among the various kinds of the above properties, the new polymers had the excellent electrical insulating properties （e.g., surface resistivity, greater than 10¹⁴Ω）, thermostability (higher than 250 ℃) and vulcanizing abilities for rubbers.