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Azobenzene‐containing liquid crystal polymers (azo‐LCPs) with reactive groups attract much attention due to the combined properties of liquid crystallinity, photoresponsivity and reactivity, which make them promising in designing intelligent photo‐driven soft actuators. Herein, a post‐polymerization modification strategy is used to prepare a series of reactive azo‐LCPs using the trans‐esterification reaction of poly(pentafluorophenyl acrylate) with functional alcohols. These reactive azo‐LCPs show good capabilities in fabricating fibers via a simple thermal‐drawing method and subsequent crosslinking reaction with diamine under mild conditions. Furthermore, the prepared fibers exhibit reversible deformation behaviors under the alternate irradiation of UV and visible light (365/530 nm). This facile synthetic strategy is expected to open up new possibilities for fabricating photo‐driven actuators. [ABSTRACT FROM AUTHOR]