The anionic alternating ring-opening copolymerizations of three bio-based aromatic monomers, eugenol glycidyl ether (EGE), dihydroeugenol glycidyl ether (DEGE) and vanilin glycidyl ether (VGE), were carried out with renewable N-acetyl homocysteine thiolactone (NHTL) using benzyl alcohol and 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP) as initiating system. This polymerization is a rare example of eugenol-based monomers used to synthesize linear polyesters. Alternating poly(ester-alt-thioether)s are obtained with number-average molar masses M n ranging from 1.1 to 10.8 kg mol-1 and dispersities as low as 1.20. The copolymer structures were carefully characterized by 1 H, 13 C, COSY, HSQC, 1 H-15 N NMR. It was found that the alternate copolymers were obtained selectively under different monomer feed ratios. In addition, the use of EGE and VGE monomers allows the preparation of multi-functional poly(ester-alt-thioether) respectively bearing allyl or aldehyde groups in each repeating unit. The copolymers display only clear glass transition temperatures higher than ambient temperature. This alternating copolymerization method offers a new chemical pathway for the valorization of bio-based aromatic compounds and expand the scope of renewable polyesters.