In this paper, the polymerization of acrolein (A) via UV-mediated atom transfer radical polymerization (ATRP) is reported. The optimization of the experimental conditions of the polymerization is investigated, and it shows that dimethyl sulfoxide as solvent, ethyl 2-bromoisobutyrate (EBIB) and fluorescein (FL) as catalyst, and [A]0/[EBIB]0/[FL]0 = 200/1/0.1 in the period of 5 h at 47 °C are suitable conditions for the reaction. In this way, the yield of the polymer is 24.5%. The glass transition temperature and melting point of polyacrolein ch...