Combining the stability of chemical crosslinking and the processability of physical crosslinking is a well-established strategy to design new materials with desirable stimuli–responsive properties. Herein, a series of azobenzenebased thermotropic liquid crystalline polyesters were synthesized by introducing mesogenic dial named 4,4ʹ-bis(6-hydroxyhexyloxy) azobenzene (BHHAB), 2-phenylsuccinic acid (PSA), and different contents of 1,2,3-propanetricarboxylic acid (PTA) as the chemical crosslinker. All these polyesters showed good thermal stability and smectic liquid crystalline phase. Wide-angel X-ray diffraction (WAXD) and the fluorescence emission spectra confirmed the existence of π–π stacking interactions as the physical crosslinking in the polymer chains, particularly at the lower content of PTA. However, when the PTA content increased, the chemical crosslinking changed the chain conformation, and thus the intensity of physical crosslinking slackened gradually. Combining the physical and chemical crosslinking, these polyesters showed the thermoplastic processability, thermal shape memory, heat-assisted healing and photo responsive behaviors. Taking advantages of these features, these multiple stimuli–responsive polymers can bring more chances for smart materials such as soft actuator.