We have used small-angle neutron scattering (SANS), and cryogenic transmission electron microscopy (cryo-TEM) to determine the structure of aggregates formed by the photoresponsive surfactants diethylene glycol mono(4',4-butyloxy, butyl-azobenzene) (C(4)AzoOC(4)E(2)) and diethylene glycol mono(4',4-hexyloxy, butyl-azobenzene) (C(4)AzoOC(6)E(2)) under different illumination conditions. At high concentrations, the self-assembly behavior of these surfactants changes remarkably in response to different radiation conditions. The trans isomers assemble into bilamellar (C(4)AzoOC(4)E(2)) and unilamellar (C(4)AzoOC(6)E(2)) vesicles, while the cis isomers (under UV light) form bicontinuous phases. These light-induced structural changes are attributed to a change in the sign of the Gaussian rigidity, which is the direct result of azobenzene photoisomerization.