Facile tuning of photophysical properties is highly desirable for boosting the performance and versatility of photoluminescent materials. In an attempt to overcome the challenge of achieving the photoswitching of multicolor luminescence on unimolecular platforms, we here report a novel hierarchical self-assembly of a cyanostilbene-naphthalimide dyad as the realization of phototunable luminescence at the unimolecular level. The work takes advantage of the photoisomerization of the cyanostilbene moiety from the Z form to its E form, which causes a morphological disorder in the molecular self-assembly and gives rise to a dual fluorescent characteristic accompanied by a progressive luminescent color conversion from yellow to green and finally to blue. Such systems with convertible multicolor luminescence might exhibit application potentials for unimolecular selective imaging and labeling, as exemplified by the cell imaging studies presented in this work.