Aggregation-induced emission (AIE) materials have gained significant attention for their unique fluorescence enhancement in the aggregated state. However, combining rigid polymers with AIE molecules to enhance luminescent properties remains to be investigated. In this work, two novel AIE-active polyarylethersulfone (PAES) derivatives are synthesized by incorporating tetraphenylethene (TPE) into either the side chain or main chain of PAES, resulting in side-chain polyarylethersulfone-tetraphenylethene (PAES-TPE) and main-chain polyarylethersulfone-tetraphenylethene (m-PAES-TPE), respectively. These derivatives are designed to investigate the influence of the rigid polymer backbone on the AIE properties of TPE. The incorporation of TPE into PAES resulted in a notable redshift in fluorescence emission compared to pure TPE. Notably, m-PAES-TPE