Achieving multicolor photoluminescence, especially white-light emission, under mild conditions based on a single fluorescent compound is a great challenge. Herein, we report a novel colorful-emission host-guest complex BPCY, which is composed of a two-arm fluorescent guest molecule (BPC) and γ-cyclodextrin (γ-CD) as the host molecule. BPC bears a unique asymmetrical donor-acceptor-donor (D1-A+∼D2)-type structure, where D1, A+, and D2 stand for the binaphthol electron donor, pyridinium electron acceptor, and coumarin electron donor, respectively. The luminescence property of BPC shows dual-sensitivity, i.e., toward the excitation wavelength and the cyclodextrin host molecule. Under certain conditions, the complex shows three different emission wavelengths, allowing the realization of multicolor photoluminescence, including red (R), green (G), and blue (B) as well as various intermediate colors by orthogonally modulating these two stimuli. In this way, nearly pure white-light emission with CIE coordinates (0.33, 0.34) could be generated. A combination of structural, spectroscopic, and computational simulation studies revealed the occurrence of synergetic mechanistic processes for the stimuli-responsive multicolor luminescence of the BPCY complex, namely, host-enhanced intramolecular charge-transfer (ICT) and host-induced restriction of intramolecular rotation (RIR). This new supramolecular complex with superior multicolor emission abilities may find wide applications in the fields of information processing and display media. Furthermore, the molecular design rationale presented here may provide a new design strategy for the development of high performance optical materials using a single supramolecular platform.