Unique elastomeric and biocompatible scaffolds were produced by the polyesterification of poly(vinyl alcohol) (PVA) and citric acid via a simple polycondensation reaction. The physicochemical characterization of the materials was done by Fourier Transform Infrared Spectroscopy (FTIR), Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), mechanical and surface property analyses. The materials are hydrophilic and have viscoelastic nature. Biodegradable, non-cytotoxic materials that can be tailored into 3D scaffolds could be prepared in an inexpensive manner. This polyester has potential implications in vascular tissue engineering application as a biodegradable elastomeric scaffold.