Cucurbit[8]uril (CB [8])-mediated cornplexation of a dicationic azobenzene in water allows for the light-controlled encapsulation of a variety of second guest compounds, including amino acids, dyes, and fragrance molecules. Such controlled guest sequestration inside the cavity of CB [8] enables the regulation of the thermally induced phase transition of poly(N-isopropylacrylamide) which is not photosensitive thus demonstrating the robustness and relevancy of the light-regulated CB [8] complexation.