A primary amine-derivatized 4-dibenzocyclooctynol (DIBO) was used to initiate the ring-opening polymerization of poly(γ-benzyl-L-glutamate) (DIBO-PBLG). This initiator yields well-defined PBLG polymers functionalized with DIBO at the chain termini. The DIBO end group further survives an electrospinning process that yields nanofibers that were then derivatized post-assembly with azide-functionalized gold nanoparticles. The availability of DIBO on the surface of the fibers is substantiated by fluorescence, SEM, and TEM measurements. Post-assembly functionalization of nanofiber constructs with bioactive groups can be facilitated easily using this process.