Prolonged exposure of polyurea to ultraviolet radiation resulted in substantial changes in the morphology and topography of the PU samples. Resulting changes are directly attributed to the significant alteration of the underlying microstructure, composed of ribbon like morphology known as hard segments, dispersed within compliant soft matrix. The scope of this research is to characterize the microstructural changes of UV exposed polyurea using atomic force microscope (AFM) along with the changes in the thermal properties of the degraded layer using a thermogravimetric analyzer (TGA). The surface roughness of the samples was found to increase with the increase in exposure duration. The crack width was found to increase along with the depth with extended exposure. This resulted from the increased shrinkage strain induced from the increased surface tensile stress arising from the subsequent photo-oxidation reaction. Crack width measured after 1.5 weeks of exposure was 2.5μm, which increased to 25μm after 15 weeks of exposure. Similarly, the longitudinal crack depth increased from 15μm after 3 weeks to 43μm after 15 weeks of exposure. Increase in surface embrittlement was observed from the topographical scans due to the increase in the polydispersity resulting from the induced photo-chemical byproducts. Surface micro-stiffness was found to increase as measured from the obtained force-distance plots, where the local modulus of the virgin sample increased from 0.2 GPa to a maximum of 12 GPa after 7.5 weeks of exposure, thereafter it remained nearly constant. Similarly, the adhesive force between the tip and the sample was found to reach minimum within 4.5 week of exposure. The phase scans obtained showed the agglomeration of the nanoscale hard segments after 1.5 weeks of exposure and remained clumped after 3 weeks of exposure all the way to 15 weeks with depletion of soft matrix. The TGA analysis of the degraded layer of the first two sections showed significant weight drop after 250°C from 4.5 to 12 weeks of exposure. The sections were comprised of highly degraded, interim and virgin layer. The thickness of the highly degraded layer and interim layer was found to be highest after 15 weeks being 15 and 20μm, respectively.