The polymerization of acrolein with phenol was studied in acidic and basic conditions for various reaction times. The initial reaction products were separated by thin layer chromatography and analyzed by infrared spectra, and then the polymer obtained by further reaction was also analyzed. The polymerization mechanism was discussed from the analytical results of the initial products and final cured polymers. Acoording to the nearly related mechanism of polymerization of acrolein with phenol, the reactions of acrolein with phenols also yielded condensation polymers like phenol-formaldehyde polymers.