This paper describes a novel approach involving the use of multifunctional initiators to initiate living free radical and cationic polymerization either sequentially or concurrently. Cationic ring-opening polymerization of oxazolines was carried out concurrently with living free radical polymerization to provide a library of amphiphilic polymers. Polymers of varying block lengths, molecular weights, and compositions and low polydispersity indices were produced. Evidence for block copolymer formation was obtained from studies involving SEC, NMR, extractions, hydrolysis, and investigation of solution properties of the polymers.