White-light emitting organic materials attract broad attention which are ascribed to their potential for applications in lighting devices and display media. Most reported organic white-light emitters rely on the combination of several components that emit different colors of light (red/green/blue or orange/blue), which may cause problems to stability, reproducibility and device fabrication. By contrast, white-light emission from single-molecule systems offers opportunities to overcome these disadvantages, meanwhile engendering white-light with high quality. Nevertheless, limited cases of white-light emission at the molecular scale reported principally concentrate on organic solvents. Herein, we designed and synthesized new bi-functional organic molecules with a symmetric donor-acceptor-donor (D-A-D) type structure with the aim to construct a single-molecule white-light emitting system in aqueous solution. Further experiments and calculations demonstrate the possibility of stacking between the pyridinium-naphthalene (PN) core and coumarin groups in the designed molecules, ascribed to hydrophobic effects, π-π stacking and donor-acceptor interactions, which could dramatically enhance the intramolecular charge transfer (ICT) efficiency along with remarkable charge transfer (CT) emission. Based on this, multicolor photoluminescence including white-light can be finely tuned in various modes including excitation wavelength, solvent polarity, temperature, and host-guest interactions. A white-light emitting (WLE) hydrogel was also facilely prepared through the dispersion of one of the compounds in a commercial agarose gelator. This innovative study helps enrich the strategies to construct single-molecule organic white-light emitting materials in aqueous medium using the self-folding behavior.