The host guest chemistry of cucurbiturils and the photochemistry of azastilbene derivatives are combined for the rationally adjusting multicolor emissions through forming different host guest complexes and their corresponding photochemical products. Cucurbit[8]uril (CB[8]) can bind with azastilbene derivatives to form supramolecular polymers emitting orange light. The supramolecular polymers further facilitate the [2 + 2] cycloaddition of C=C bonds in azastilbenes by UV irradiation, emitting blue light. Different from CB[8], cucurbit[7]uril (CB[7]) encapsulates azastilbene derivatives to form a dumbbell-shaped host-guest complex, emitting dark-purple light. This dumbbell-shaped host guest complex undergoes cis-isomerization after UV irradiation, thus emitting green light. Therefore, this strategy is promising for fabricating advanced stimuli-responsive fluorescent materials.