Electrospun polyglyconate (Maxon) and its blends with proteins such as gelatin and elastin, with a spatially designed layer structure, were prepared as potential scaffolds for vascular tissue engineering. In vitro biodegradation of the electrospun tubular protein/Maxon scaffolds in phosphate buffered saline (pH = 7.3) was studied for the first time. The biodegradation is manifested by uptake of the PBS medium by the hydrophilic proteins and also by the mass loss due to the removal of degraded fragments and uncrosslinked proteins from the matrices. The effect of degradation on the structure-property relations was evaluated by IR, XRD, and DSC analyses of the aged scaffolds. The degradation of amorphous phase of Maxon in the early stages of aging has resulted in an increase in the crystallinity of the polymer. SEM analysis indicated a significant change in nanofiber morphology and fiber-breaking. The mass loss and fiber breaking have negatively impacted the mechanical properties and the effect was maximum at 15-20 days of aging. The scaffold containing low molecular weight buffer soluble elastin revealed relatively better degradation properties compared to that containing high molecular weight buffer insoluble elastin.