This article presents a new strategy to achieve white-light emission from single tetraphenylethylene-substituted pyrenes (TPE-Pys) with aggregation-induced emission (AIE) characteristics. TPE-Pys were synthesized by a Pd-catalyzed coupling reaction of a boronic acid or pinacol ester of pyrene and tetraphenylethylene (TPE) derivatives and showed multicolor emission by introducing different substituents on the phenyl rings of TPE. TPE-Pys with a TPE unit at the 1-position and asymmetric TPE units at 2,7-positions show dual fluorescence in THF/water mixtures to realize white-light emission with CIE coordinates of (x = 0.30 and y = 0.41) and (x = 0.21 and y = 0.16), respectively. The structure-property relationship of TPE-Pys were investigated to elucidate the origin of the white emission. The results showed that due to the weak electronic interaction of pyrene and its chromophoric units at the 2,7-positions and the constraint of the rotation of the TPE unit at the 1-position of pyrene, each component can exhibit its own emission color. The combination of appropriate colors gives rise to white-light emission. Such a principle of molecular design may open a new avenue for preparing advanced multicolor and multifunctional optical materials for organic electronics.