In this study, we have successfully designed and synthesized a series of crown ether-CPP hybrid multimacrocycles and explored their supramolecular properties, photophysical behavior, and biological applications. The integration of crown ethers into the CPP framework not only improves solubility and enhances fluorescence quantum yield but also introduces new binding sites that facilitate selective host-guest interactions. Notably, the trimacrocyclic hybrid adopts a molecular tweezer-like conformation, leading to a five-fold increase in fullerene binding affinity compared to its bismacrocyclic counterpart. This enhanced host-guest recognition behavior, supported by fluorescence quenching titrations and density functional theory (DFT) calculations, provides new insights into the design of high-affinity supramolecular receptors.