Tiglic acid esters are naturally derived olefins of pleasant odor but incapable of undergoing free-radical polymerization due to the steric hindranes conferred by the beta-methyl group. In an effort to incorporate these green olefins in well-defined (co)polymers, we first established that methyl tiglate, the simplest tiglic acid ester, could not be polymerized using controlled polymerization techniques either, and we then introduced it in a methacrylate monomer, 2-(methacryloyloxy)ethyl tiglate (MAET), which could smoothly undergo group transfer polymerization (GTP) to yield linear polymers of narrow molecular weight distributions. Subsequently, amphiphilic and double-hydrophobic block copolymers, as well as a star polymer of MAET were obtained by its sequential GTP with 2-(dimethylamino)ethyl methacrylate, methyl methacrylate, and ethylene glycol dimethacrylate, respectively. Finally, polyMAET was selectively oxidized.