The less frequent lower critical solution temperature (LCST) phenomenon has attracted extensive attention due to the foresighted application in smart materials. Nevertheless, the existing LCST-type materials are mainly dominated by a few polymers with specific moieties due to the damped hydration at a higher temperature and the lack of reversible regulations of the corresponding temperature sensitivity. Herein, an unanticipated and reversibly photo-responsive LCST behavior was uncovered in the BSC4/Azo-4 assembly solution. Such behavior arose from the host-guest binding between BSC4 and Azo-4 in an aqueous solution since neither the guest nor host alone exhibited an LCST property. Ascribing to the distinct π-π stacking between the trans- and cis-isomers of Azo-4, a reversible regulation of LCST behavior was achieved by irradiating UV and blue light alternately. Our study demonstrated the complexity and possibility of supramolecular self-assembly, opening a new avenue in the fabrication and adjustment of LCST-type materials in the future.