Conductivity switching was observed in the LB films of supermolecules having phenylazonaphthalene, alkyl chains, and pyridinium(TCNQ)(2) as switching, transmission, and working units. respectively. The utilization of phenylazonaphthalene shifts the wavelength of the control light for the conductivity switching toward a longer wavelength region compared with the case of azobenzene as a switching unit.