The electrostatic layer-by-layer technique provides a convenient way to control the construction of ultrathin films at nano-scale ranges and can be easily obtained. It can be also applicable to fiber substrate with dye compounds. We have fabricated multilayer dye films using diazonium resin and three couplers, which are prepared by self-assembly approach. This method is based on layer-by-layer deposition using electrostatic attraction between oppositely charged ions. Beside, the diazo coupling reaction proceeded to form azo dye layer on the PET fibers the same time. The corresponding results of the multilayer films have been discussed on the level of color strength (K/S).