Four vinyl-functionalized azobenzene-based liquid crystals (LCs) were synthesized and characterized by H-1 and C-13 nuclear magnetic resonance, and Fourier transform infrared spectroscopies. Their thermal stability was measured by thermogravimetric analysis and their thermotropic liquid-crystalline properties were determined by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and X-ray diffraction (XRD). The azobenzene-based LCs displayed a nematic phase whereas those mesogens having an extra phenyl group developed lamellar mesophases of the SmA and SmC types. Combined with non-photoactive monomers, these vinyl-functionalized azobenzene-based mesogens can be used to prepare photo-active side-chain liquid crystal elastomers having potential use in optical actuators.