The combination of polyelectrolytes and surfactants has been the focus of intense fundamental and applied research in the past years due to their numerous industrial applications. When different ratios of polyelectrolytes and surfactants are added in solution, a combination of electrostatic and hydrophobic interactions occur that lead to the formation of different types of aggregates. Our work focuses on the interactions of stoichiometric amounts of poly(styrenesulfonate) (PSS) with dodecyltrimethylammonium bromide (DTAB) which form a highly ordered lamellar structure that was characterized by X-ray diffraction. We used an azobenzene-trimethylammonium bromide surfactant (Az-surf) as a photoresponsive material, in varying ratios to DTAB, to disrupt the interaction between PSS and DTAB in the lamellar structure. Azobenzene, and various derivatives, can undergo cis-trans isomerization upon excitation with UV and blue light. This isomerization will allow enough structural change/disruption in the morphologies of the lamellar structures that can be then detected.