AbstractThe introduction of functionality is essential to the surface, bulk and mechanical properties of poly(diene‐styrene). In this work, copolymerizations of hydroxyl (My‐OH) and epoxide (My‐EPO) functionalized myrcenes with styrene by a solvent‐free reversible addition fragmentation chain transfer polymerization route have been performed. In both cases, the copolymerizations were processed with functional diene preferentially inserted (rMy‐OH/rSt, 1.28 ± 0.02/0.81 ± 0.02; rMy‐EPO/rSt, 1.15 ± 0.01/0.91 ± 0.02), providing a series of composition drifted copolymers with controlled functionality degree and molecular weight by feeding ratios of comonomer and chain transfer agent. The copolymers have remarkably low contact angles with water, an indication of potentially good miscibility with polar additives. In addition, the in‐chain included hydroxyl and epoxide groups could further provide a very versatile ‘intermediate’ that can be used to prepare various functional polymers, block and graft copolymers. © 2022 Society of Chemical Industry