Poly(epsilon-caprolactone)-block-poly(ethylene glycol)-block-poly(epsilon-caprolactone) (PCL-b-PEG-b-PCL) triblock copolymers with biotin groups at the junction points were synthesized based on a; combination of click chemistry and ring-opening polymerization (ROP). Alkyne-functionalized PCL-b-PEG-b-PCL triblock copolymers were synthesized by using alkyne-functionalized PEG as macroinitiators in ROP of epsilon-caprolactone. Click chemistry was employed in the synthesis of the biotinylated triblock copolymers. Gel permeation chromatography and H-1 NMR results all indicated successful synthesis of well-defined triblock copolymers. The triblock copolymer chains can self-assemble into micelles in aqueous solution. The PCL blocks form the cores of the micelles and the hydrophilic PEG blocks form the coronae. The biotin moieties distribute at the interface of the micelles. Upon addition of avidin to the micellar solution, micelles aggregated together forming micellar aggregates due to the interaction between avidin and biotin. The avidin/HABA competitive binding assay also proved the bioavailability of the biotinylated micelles to avidin.