A series of copolymers with varying degrees of alternation are synthesized by free-radical polymerization from 2,3,4,5,6-pentafluorostyrene (PFS) and propargyl-containing styrene derivatives. The degree of alternation varied with the electronic nature of the styrene derivative: random copolymers were obtained using monomers with electron withdrawing moieties, whereas increasingly alternating copolymers were obtained by increasing the electron donating nature of the substituent. The copolymers could be functionalized in an orthogonal fashion using a nucleophilic substitution (with thiols) to functionalize PFS and the copper-catalyzed 3 + 2 cycloaddition between azides and the alkyne of the propargyl groups. This methodology allows for the facile synthesis of functional alternating copolymers.