The self-assembly behavior of two sandwich-type mixed (phthalocyaninato)(porphyrinato) europium double-decker complexes, namely Eu(Pc)(TCIPP) [Pc = phthalocyaninate; TCIPP = meso-tetrakis(4-chlorophenyl)porphyrinate] (1) and optically active (R)- and (S)-EuH[Pc(OBNP)(2)][TCIPP)] [Pc(OBNP)(2) = phthalocyaninate with two aromatic chiral binaphthayl units attached at the nonperipheral positions.] (2), has been comparatively Studied. In addition, a hydrophilic additive with intense adhesive ability, sodium carboxymethylcellulose (CIVIC), was also introduced onto the sandwich-type self-assembly systems to combine with double-decker molecules to induce additional hydrophilic/hydrophobic interaction. In the absence of the additive CMC, the double-decker molecules of I self-assemble into nanobelts in mixed solvent of chloroform and methanol. Introduction of two aromatic chiral binaphthayl units onto the nonperipheral positions of phthalocyanine ligand in the sandwich-type mixed double-decker complex 2 leads to the formation of tubal nanostructures. Observation of significant difference in the circular dichroism (CD) spectra of (R)- and (S)-2 in chloroform from their aggregates dispersed in methanol confirms the effective intermolecular interaction due to the interplay of pi-pi interaction between adjacent double-decker molecules with chiral discrimination among chiral side chains at supramoleular level. With addition of CMC, cooperation of intrinsic intermolecular pi-pi interaction with additionally introduced hydrophilic/hydrophobic interaction between adjacent double-decker molecules induces the formation of nanoscale hollow spheres at 45 degrees C during the self-assembly process of 1 and 2.