Commonly poly(pentafluorophenyl acrylate) is synthesized by free radical polymerization of the monomer pentafluorophenyl acrylate. 
Additionally, pentafluorophenyl acrylate can be successfully polymerized by RAFT polymerization yield homopolymers, copolymers, or block copolymers.
It has been shown that poly(pentafluorophenyl acrylate) can also be prepared by pulsed plasma deposition.