Molecular tiling has been developed as a novel technique for controlled molecular arrangements in two-dimensional plane. The ICA isotherm of a cyclophane derivative with eight alkyl chains has a limiting area apparently smaller than the cyclophane core, indicating that the cyclophane core was deformed at high pressures. In contrast, the equimolar-mixed monolayer of the cyclophane derivative and a guanidinium amphiphile on an aqueous naphthalene guest showed an isotherm with a limiting area comparable to the cyclophane core. A drastic increase in surface fluorescence due to the guest insertion was also observed. These results strongly indicate that the cyclophane derivative formed a rigid complex with the guanidinium amphiphile and aqueous naphthalene derivative. The formed complex can be a good candidate for a tiling unit.