A multiply photoactive compound has been developed based on quaternized 1,2-bis(4'-pyridyl)ethylene, which exhibits a hierarchical photoreaction by controlling light intensity. Weak ultraviolet light can effectively promote the cycloaddition reaction with fluorescence enhancement, while stronger ultraviolet light can stimulate a complex response of cycloaddition and electron-transfer which shows turn-off luminescence and coloration. Photofacilitated bleaching of the colored products has been observed for the first time in the pyridinium family.