The aggregation behavior in water of the fluorinated phosphocholine-derived single-chain amphiphile C8F17C2H4OP(O)(2)(OC2)-O---H4N+ (CH3)(3) can be drastically modified by co-dispersion with the fluorinated alcohol C8F17C2H4OH. Depending on the alcohol/phosphocholine ratio, flat or loosely wound bilayer sheets, elongated rolled up microstructures, or rigid platelets were observed to form, instead of the vesicles that are obtained when the phosphocholine derivative is alone. These results are discussed in terms of packing parameter, anisotropic packing, and enhanced tendency for fluorinated chains to promote crystallization.