Polydioxanone (PDS) is a colorless, crystalline, bioabsorbable polymer that was first developed specifically for wound closure sutures. The compatibility, degradation rate, and mechanical properties (including shape memory) of PDS are of interest when considering the design of tissue engineering scaffolds. This research presents the electrospinning of PDS to fabricate unique nanofibrous structures for a variety of biomedical applications. Electrospinning is a polymer processing technique that utilizes an electric field to form fibers from a polymer solution or melt and allows the fabrication of nanofibrous non-woven structures. Results demonstrate the ability to control the fiber diameter of PDS as a function of solution concentrations and the fiber orientation with our prototype electrospinning apparatus. The results also show dependence between the fiber orientation and the elastic modulus, peak stress, and strain to failure of PDS in a uniaxial model.