In the present paper ZnCuInS/ZnS core/shell quantum dots were prepared with the particle size of 3.2 nm. Its radiation is based on the donor-acceptor pair transitions, not the band edge emission. According to the measurement of photoluminescence spectrum emitted by ZnCuInS/ZnS core/shell quantum dots, the emitting peak of 620 nm and the full width at half-maximum of 95 nm were achieved as red emitter; meanwhile, organic poly(N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)benzidine) (Poly-TPD) film was deposited and used as cyan-emitter with the peak of 480 nm. Two structures of Poly-TPD were analyzed and discussed according to the photoluminescence spectrum. Two wavelengths are complementary color. Therefore, two films were deposited one by one as bilayer emitter to obtain the complementary emission. After the suitable bias was applied on the films, the white emission was achieved with the Commission Internationale de l’Eclairage (CIE) chromaticity coordinates of (0.336, 0.339) and color rendering index of 92. Therefore, the bilayer-structure is a promising candidate for white light emitting diodes fabrication.