Over the past 10 years poly‐(polyol alkanoate)s elastomers have intensively been investigated due to their extraordinary potential for soft tissue engineering applications. In this work, a family of novel hyperbranched elastomers based on pentaerythritol and adipic acid, modified with PEG of 200 and 400 Da, is synthesized. The polymers are obtained by a simple 2 steps thermal process that avoids the use of toxic catalysts. Noteworthy, elastomers properties can be finely tuned by adjusting the molar ratio of monomers and curing conditions. The elastomers, which are fully characterized by standard methods, show excellent results in the in vitro controlled release of Paclitaxel. Cell culture assays indicate that all materials are able to inhibit lung cancer cell proliferation and that the release of Paclitaxel reduce cancer cell viability, indicating that the elastomers prepared hereby are good candidates for their use as eluting systems in long term cancer treatment. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1199–1209