Abstract: Molecular self-assembly process of biological building blocks enables the formation of complex architectures and machinery; our interest in studying amphiphilic systems is due to their potential development as supramolecular systems capable of interacting with lipid membranes. Inspired by the pioneering work of Kunitake et. al. and oriented to establish a relationship between structure and morphology of amphiphilic systems, we have started with the synthesis and evaluation of new non-ionic amphiphilic based on azobenzenes. In order to investigate the physicochemical properties of systems with potential application as membrane modulators, it is necessary to evaluate the capability of the system to form liquid crystal mesophases. Both non-ionic amphiphiles presented a liquid crystal behavior. In order, to establish the importance of the connector, compounds with a hydroxi head directed attached to the rigid segment were also studied. Although the structural changes are minor, the position of the hydrophobic tail or the presence of the connector between the polar head and rigid segment led to significantly different stabilities of the mesomorphic transition temperatures observed. Fig1. Non-Ionic Amphiphiles evaluated. Herein, it is presented the thermal and morphological characterization of new non-ionic Azobenzene Amphiphiles evaluated by Differential Scanning Calorimetry (DSC) and Polarizing Optical Microscopy (POM).