Photoalignment technology is serving as an emerging technology for programming liquid crystalline polymer (LCP) materials due to its advantages including noncontact, high resolution, spatial control, programmability, and high efficiency. In this review, we report the research progress in implementing polarized light to design the anisotropy of LCPs, which is categorized based on the photoalignment mechanisms. The alignment approaches and the different stimulus‐responsive behaviors of the materials after photoalignment are discussed. Additionally, we have summarized the applications of photoaligned LCPs such as liquid crystal displays, optical components, intelligent soft actuators, and beyond. Finally, the challenges and future directions of the technology are outlined.