Hybrid Langmuir-Blodgett (LB) films were fabricated by transferring pure monolayers of an azobenzene derivative having a TCNQ (7,7,8,8-tetracyanoquinodimethane) moiety (APT) and then 1:1 mixed monolayers of cyanine/APT on solid substrates. The hybrid LB films have binary output modes. The alternate irradiation of UV and visible light yielded reversible cis-trans isomerization of APT, which was accompanied by the electrical conductivity switching associated with APT molecules and the change in the optical properties of the films due to the development of the J-band of the cyanine dye (CY). The order of the sequential deposition of the APT pure monolayers and the 1:1 mixed monolayers of CY/APT plays an important role in realizing the hybrid LB films with binary output modes.