Photosurfactants (PS) demonstrate the combined ability to change their shape upon irradiation with light and self-organise into polymolecular assemblies. However, the phase behavior of PS is not well-established and there have been limited reports of their lyotropic liquid crystal (LLC) phase formation. Here, we will undertake a strategic structure-activity study to identify the key structural features required to unlock the LLC phases of azobenzene PS. Small-angle neutron scattering (SANS) will allow us to directly observe the size and shape of PS aggregates as a function of increasing concentration, and thus observe how they grow and begin to assemble into LLC phases. The objectives of this study include to: (i) determine the effect of photoswitching on the polymolecular structures formed; (ii) track the self-assembly and growth of PS aggregates from isolated micelles to LLC phases.