We have developed a series of azobenzene liquid crystals (azo LC) compounds, both multicomponent as well as single component, that possess room temperature nematic and smectic phases. Some of these materials have a wide mesophase temperature range which makes them useful for a variety of practical applications. Two main strategies were used for controlling the temperature range of these mesogenic azo LC materials: 1) chemical modification of azobenzene molecules with different terminal pendants; and 2) development of multicomponent compositions. These materials were highly photosensitive exhibiting nonlinear refraction and transmission at nanowatt/microwatt power levels. Physical, electro- and nonlinear-optical parameters of many of these materials have been characterized in detail.