The novel biomaterial poly(glycerol sebacate) (PGS) holds great promise for tissue engineering and regenerative medicine. PGS is a rubbery, degradable polymer much like elastin; however, it has been limited to cast structures. This work reports on the formation of PGS nanofibers in random non-woven mats for use as tissue engineering scaffolds by coaxial core/shell electrospinning. PGS nanofibers are an inexpensive and synthetic material that mimics the chemical and mechanical environment provided by elastin fibers. Poly(lactide) was used as the shell material to constrain the PGS during the curing process and was removed before cell seeding. Human microvascular endothelial cells from skin (HDMEC) were used to evaluate the in-vitro cellular compatibility of the PGS nanofiber scaffolds.