The synthesis and photophysical properties of well‐defined polymer‐rhenium(I) hybrid materials is described. Reversible addition‐fragmentation chain transfer polymerization of pentafluorophenyl acrylate yields a parent homopolymer that serves as a reactive scaffold for the preparation of a series of new statistical copolymers containing pendent pyridyl functional groups in conjunction with various other repeat unit species. Attachment of [Re(CO)3(phen)]+ fragments via coordination through the pendent pyridyl groups yields the hybrid metal‐copolymer materials. Photophysical studies confirm successful rhenium coordination as judged from the absorption and emission profiles of the hybrid materials and further verify that the polymeric scaffold has no discernable effect on the luminescent properties of the coordinated rhenium species.