ABSTRACT To examine the impact of side-chain flexibility on the photosensitivity of polyimide liquid crystal (LC) alignment films, two polyimides (OD-HAB-CA and OD-HAB6-CA) were synthesised. OD-HAB6-CA contains flexible hexamethylene side chains. This study demonstrates that the OD-HAB-CA alignment film can induce LC molecular alignment after 80 min of non-polarised ultraviolet light (NPUVL) irradiation. In contrast, the OD-HAB6-CA alignment film can achieve the same result after only 35 min of irradiation. This suggests that the flexibility of the side-chain can significantly improve the photosensitivity of the alignment film and shorten the required irradiation time. In addition, OD-HAB-CA and OD-HAB6-CA exhibit good thermal stability and light transmittance properties. The resulting LC cell have pretilt angles of 0.2° and 0.5°, respectively, which are suitable for in-plane switching mode LCDs.