Self-assembled molecular aggregates of fluoroalkyl end-capped N-(1,1-dimethyl-3-oxobutyl)-and N,Ndimethyl-acrylamide oligomers in methanol were found to interact with phthalocyanines as guest molecules to exhibit good solubility. On the other hand, the corresponding nonfluorinated oligomers were not effective in solubilizing phthalocyanines under similar conditions. In these oligomers, fluorinated N-(1,1-dimethyl-3-oxobutyl)acrylamide oligomers were more effective in solubilizing phthalocyanines in methanol. Self-assemblies formed by fluorinated oligomer-phthalocyanine complexes are applied to the surface modifications of polystyrene (PS), and the modified PS surface exhibited not only a strong oleophobicity imparted by fluorine but also good hydrophilicity. Thus, these fluorinated molecular aggregate-phthalocyanine systems are suggested to have high potential for new fluorinated functional materials through their excellent properties imparted by fluorine and phthalocyanines.