A family of copper and zinc phthalocyanine-based amphiphililes possessing racemic and optically active diol units, (rac)-ZnPc(OH)(16), (rac)-CuPc(OH)(16), and (S)-CuPc(OH)(16), have been synthesized. The self-assembling properties of these amphiphiles in aqueous solution have been studied by W-vis, Fourier transform infrared (FTIR) and circular dichroism (CD) spectroscopies, X-ray diffraction (XRD) patterns, and transmission electron microscopy (TEM). Only the copper complexes produced fibrous assemblies from aqueous solutions through two noncovalent bondings: pi-pi interaction among phthalocyanine rings and hydrogen bonds among diol units. The formation of fibrous assemblies strongly depends on the central metal of the phthalocyanine complex. The optically active (S)-CuPc(OH)(16) is stacked and arranged in a left-handed helix. The chirality of diol units in (S)-CuPc(OK)(16) also affects the intercolumnar lattice of phthalocyanine stacks.