With the growing demands in flexible electronics, the development of plastic and organic materials has gained increased interest. In this focus review, the design concepts and recent advances of organic liquid crystalline materials in optoelectronic devices were introduced. Thermotropic liquid crystalline materials are categorized into three types: calamitic, discotic, and cholesteric types according to the structures of rodâlike, diskâlike, and chiral rodâlike molecules, respectively. Numerous liquid crystalline materials have been successfully incorporated in organic electronic devices. Notably, smectic liquid crystals hold great promise as semiconducting channel, floating gate electret, and charge transporting interlayer in fieldâeffect transistors, nonvolatile memory, and photovoltaics, respectively. This review sheds light on the great potential and importance of the organic liquid crystalline material for optoelectronic device applications.