Amphiphilic block copolymers of poly(ethylene oxide) (PEO) and poly(fluorooctyl methacrylates) were synthesised by atom transfer radical polymerisation of semifluorinated methacrylates such as 1H,1H-perfluorooctyl methacrylate, and 1H,1H,2H,2H-perfluorooctyl methacrylate using PEO macroinitiators. The use of mono- and difunctional initiator led to AB and ABA block copolymers with controlled molecular weights. The linear time dependence of In([M](o)/[M]) is consistent with a controlled polymerisation i.e. first-order in monomer concentration. Various block copolymers could be prepared by varying the ratio of monomer to macro-initiator. The copolymers self-assembled in chloroform to form micelles, which was evidenced by dynamic light scattering and transmission electron microscopy. Different morphologies of spheres and rods were observed by changing the copolymer composition. In addition, these surfactants lower the interfacial tension between water and supercritical carbon dioxide to stabilise water-in-carbon dioxide emulsions.