Polymeric nanofibers are promising in tissue engineering applications due to its dimensional similarity to natural collagen. While these nanofibers can be generated easily via electrospinning, they lack the bioactive motifs to guide cellular behavior. Efficient method to functionalize these nanofibers after electrospinning is important for improved cellular performance. In this project, 4-dibenzocyclooctynol (DIBO) and its derivatives were used as initiators for ring-opening polymerization to yield different kinds of polymers like DIBO-PBLG, DIBO-PCL, DIBO-PLA , DIBO-(P(CL-co-OPD)) and so on. DIBO group at the chain terminal of polymers enables fast, efficient and catalyst-free functionalization of the polymer. For further applications of these materials, nanofiber based scaffolds were generated via electrospinning. The generated nanofibers bearing active DIBO groups on the surface are capable of post-fabrication functionalization in aqueous solution without catalyst. Within a few minutes of immersion, these fibers were functionalized according to fluorescence staining. The removal of copper catalyst reduces the potential risk due to the toxicity of copper ion. The yielded scaffolds were used for neuron engineering, soft tissue repair and protein stabilization. Moreover, combined with other types of efficient chemical methods, di-functionalized and tri-functionalized nanofibers were constructed for the investigation of synergistic effect in tissue engineering.