In this paper we report successful simple synthesis of unique elastic polyesters by carrying out catalyst-free polyesterification of multifunctional non-toxic monomers: 1,8-octanediol (01), citric acid (CA) and sebacic acid (SA). The chemical, physical, and surface chemical properties of the resulting copolyester polyoctanediol citrate/sebacate [p(CCS)] have been investigated. This new material was characterized by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-ToF-MS), nuclear magnetic resonance spectroscopy (NMR), thermal analysis (TA), mechanical tests, photo-acoustic Fourier-transform infrared spectroscopy (PA-FTIR), X-ray photoelectron spectroscopy (XPS) and swelling experiments. We demonstrate that the chemical structure, morphology, physical integrity and surface chemistry of the synthesized co-polymer can be controlled by simply varying the initial acid concentration (CA/SA) in the pre-polymer. This novel p(OCS) polymer exhibits versatility in mechanical properties, hydration and hydrolytic degradation as determined by the chemical structure of the polyester elastomer. (C) 2009 Elsevier Ltd. All rights reserved.