This article presents the synthesis of a new family of synthetic isotactic polyesters derived from poly((S)-3,3-dimethylmalic acid) (PDMMLA). These polyesters are prepared via the lactone route bearing functionalized groups in its main or side chain. The aim of this work is twofold: metabolism and stereochemistry. First, the synthesis of these new polyesters is chosen to provide biodegradable polyesters biocompatible and bioassimilable by the human body. Next, the molecular chain of this family contains a stereogenic center in the aim to provide 100% isotactic homopolymers and copolymers (statistical and block). Finally, these polymers have been characterized by several analytical techniques: FTIR, H-1 and C-13 NMR, SEC, DSC, and TGA. The greatest importance will be given to the C-13 NMR and DSC to principally confirm the stereoregularity and crystallinity of these stereopolyesters. (C) 2015 Wiley Periodicals, Inc.