Amphiphilic centipede-like brush copolymers with biodegradable poly(epsilon-caprolactone) and poly(ethyl ethylene phosphate) side segments were prepared by a one-pot syntheses strategy. The syntheses combined ring-opening polymerization of 2-ethoxy-2-oxo-1,3,2-dioxaphospholane through a "grafting from" strategy and "click" reaction with alpha-propargyl-omega-acetyl-poly(epsilon-caprolactone) through a "grafting to" strategy, using multifunctional poly(tert-butyl methacrylate)-co-poly(2-hydroxy-3-azidopropyl methacrylate) that bears hydroxyl and azide groups from junction points. The reactions Eire controllable, and the structure of obtained centipede-like brush copolymer is well characterized. These brush copolymers Eire amphiphilic and self-assemble into spherical micellar Structure in aqueous solution with critical aggregation concentration around 10(-3) mg mL(-1) and average diameters of 50-90 nm. Such micelles formed from centipede-like brush copolymers can be used as drug carriers for biomedical applications.