This article discusses an effective route to prepare amphiphilic diblock copolymers containing a poly(ethylene oxide) block and a polyolefin block that includes semicrystalline thermoplastics, such as polyethylene and syndiotactic polystyrene (s-PS), and elastomers, such as poly(ethylene-co-1-octene) and poly(ethylene-co-styrne) random copolymers. The broad choice of polyolefin blocks provides the amphiphilic copolymers with a wide range of thermal properties from high melting temperature similar to270 degreesC to low glass-transition temperature similar to -60 degreesC. The chemistry involves two reaction steps, including the preparation of a borane group-terminated polyolefin by the combination of a metallocene catalyst and a borane chain-transfer agent as well as the interconversion of a borane terminal group to an anionic (-O K) terminal group for the subsequent ring-opening polymerization of ethylene oxide. The overall reaction process resembles a transformation from the metallocene polymerization of alpha-olefins to the ring-opening polymerization of ethylene oxide. The well-defined reaction mechanisms in both steps provide the diblock copolymer with controlled molecular structure in terms of composition, molecular weight, moderate molecular weight distribution (M-w/M-n < 2.5), and absence of homopolymer.