The invention discloses a method for separating perfluoroalkylethyl acrylate and perfluoroalkylethylene, comprising the following steps: (a) a mixture of perfluoroalkylethyl acrylate and perfluoroalkylethylene and an entrainer are added, according to the mass ratio of 1:0.05-0.2, into a rectifying tower to carry out azeotropic distillation at the azeotropic distillation temperature of 90-130 DEG C at the vacuum degree of 0.03-0.07 MPa, so as to obtain an overhead fraction and a bottom residue, and the bottom residue is collected to obtain a perfluoroalkylethyl acrylate product; (b) the overhead fraction obtained in the step (a) undergoes standing for layering so as to obtain an upper-layer product and a lower-layer perfluoroalkylethylene crude product; and (c) the perfluoroalkylethylene crude product is purified by reduced pressure distillation so as to obtain a perfluoroalkylethylene product. The method provided by the invention has advantages of simple process, good separating effect, low cost, safety and environmental protection.