Polymeric nanofibers are attractive for a number of regenerative medicine applications. However, historically nanofibers have been difficult to derivatize with peptides using methods that are translationally relevant. Efficient chemical methods designed to controllably derivatize degradable polymeric nanofibers with peptides and carbohydrates would be widely applicable to the biomaterials community. In our research, we have sucessfully utilized 4-dibenzocyclooctynol (DIBO) and its derivatives to initiate the ring-opening polymerization of a number of different monomers like lactide, e-caprolactone and several copolymer blends. The presence of a DIBO group at the chain end of the polymers enables fast, efficient and metal-free post-electrospinning functionalization with complemetary bioactive species posessing azide groups. We will describe the use of our nanofiber based scaffolds in neural engineering, soft tissue repair and protein stabilization.