Liquid crystal (LC) is a kind of functional soft matter featured by self-assembly and stimuli responsiveness. It is widely known as a fundamental material for current mainstream information display industry. With the development and innovation of LC theory and technology, understanding on such a material system has been significantly extended. Recently, the manipulation of LC microstructures has been flexibly enabled via a photoalignment technique, and the research focus has been gradually transitioned from traditional displays to advanced LC photonics. It is expected to provide great opportunities in the fields of planar optics, structured light fields, optical cross connection, and mode division multiplexing optical communications. This review presents the latest works of the Research Center for Liquid Crystal and Photonics of Nanjing University in the field of photoalignment-enabled LC microstructures and photonic applications. To be specific, LC hierarchical architectures, optically addressed spatial light modulators, and LC telecom/terahertz elements are separately discussed.