Poly[(styrene)-rotaxa-(crown ether)]s were synthesized by free radical polymerizations of styrene in the presence of crown ethers using bulky ＇blocking group＇ initiators to ensure end-capping for prevention of dethreading. These statistical processes produced only low threading yields, but up to 26% cyclic by mass with large crown ethers. The poly[(styrene)-rotaxa-(crown ether)ls ＇emulsified＇ in protic solvents such as methanol and water. The dispersion polymerization of styrene in methanol or water using ＇42-crown-14＇ (＇42C14＇) indicated that threading provided stability of the polyrotaxane micelles in such solvents through hydrophilic-hydrophobic phase separation. DSC investigations indicated that the threading prevents the crystallization of the crown ether and allows phase mixing to some extent, since two altered T-g＇s were observed.