ATRP using poly(propylene oxide) monofunctional macroinitiator was carried out with solketal methacrylate (SMA) and the non-reactive PPO having two N-3 terminal groups was removed by dissolution in an excess of n-hexane. The resulting azido terminated AB diblock copolymer was 'clicked' with an alpha-alkyne fluorinated compound, followed by acid hydrolysis of the SMA units, a triphilic ABC triblock copolymer was prepared. ATRP of SMA with a difunctional PPO macroinitiator to give ABA triblock copolymer was also carried out. The terminal Br was again exchanged with N3, 'clicked' with the a-alkyne fluorinated compound and likewise hydrolyzed to give a triphilic CABAC pentablock copolymer, i.e., hydrophilic, oleophilic, and fluorophilic blocks were combined.