4-(4-(4-(Didodecylamino)phenylazo)phenyl acid is synthesized, and its Langmnir-Blodgett (LB) monolayer is successfully fabricated. The drastic changes in electronic spectra of this compound are found in acidic solution and in LB monolayer upon exposure to HCl vapor (mainly the decrease in absorption at 416 nm and great increase at 540 nm). The UV-visible and infrared spectra reveal a mechanism of protonation to either azo group or amino group. This phenomenon has been suggested to have its prospective application in fundamental interfacial materials for pH sensors.