beta-Cyclodextrin (beta-CD)-ended linear poly(N-isopropylacrylamide) (beta-CD-PNIPAM) and Frechet-type benzyl ether dendron with an azobenzene group (Gx-Azo) at the apex site form noncovalently connected amphiphiles (NCCAs) by inclusion complexation between the azo group and beta-CD. The NCCAs self-assemble into vesicles in water. Optical switching of the assembly and disassembly is realized by alternating visible and UV irradiation, which causes the isomerization of the azo groups and their consequent complexation and decomplexation with beta-CD. The structure and morphology of the vesicles were characterized by dynamic light scattering (DLS), static light scattering (SLS), SEM, TEM, and AFM. These photoresponsive vesicles can further respond to heat stimuli resulting in reversible aggregation and disaggregation of the vesicles.