Effects of a small functional group, cyano, on the supramolecular polymerization of fan-shaped monomers were investigated. When cyano groups are replaced by hydrogen atoms, the resultant monomers surprisingly fail to undergo supramolecular polymerization and exist as monomers in methylcyclohexane (MCH). Moreover, in the mixed monomer systems, we successfully visualized a small difference in the self-assembling behaviors, which was dependent on the number of cyano groups.