Many novel areas of biological investigation require the patterned immobilization of bioactive ligands. In this work, easily modified thin films of poly[(pentafluorophenyl methacrylate) (PFM)-co-(ethylene glycol diacrylate) (EGDA)]are synthesized by initiated chemical vapor deposition (iCVD). PFM possesses a pentafluorophenyl ester side chain moiety, which is an excellent leaving group for the attachment of nucleophilic ligands by a single reaction step, while the EGDA functions as a crosslinking agent. Patterned surface modification through microcontact printing of fluorescently labeled amines that remain immobilized after repeated solvent rinses is demonstrated. Bulk modification of the copolymer with aminoethoxyethanol, which results in a ≈20° reduction in the observed contact angle with water, is also shown.