Synthesis of an a,beta-alkyl branched polyester, i.e., poly(2-methyl-3-hydroxyoctanoate), has been accomplished via anionic polymerization of alpha-methyl-beta-pentyl-beta-propiolactone mediated by supramolecular complexes of potassium methoxide or potassium hydroxide, respectively. The structure of resulting polymers has been established by electrospray ionization multistage mass spectrometry (ESI-MSn), FT-IR, NMR, and GPC analyses. Previously proposed addition-elimination mechanism of the polymerization of beta-lactones containing alpha-hydrogen by alkoxide anion has been confirmed to operate also in the case of beta-lactone having alkyl substituents in both alpha and beta positions.