The integration of aggregation-induced emission (AIE) and two-photon absorption (2PA) into one molecule is very important because such a combination would endow the material with a synergetic effect for diverse and broader applications. Herein, two regioisomers based on perylene diimide and anthracene moieties are designed and synthesized. The as-prepared compounds exhibit distinct AIE and 2PA properties, where the bay-substituted one exhibits common AIE and 2PA properties, while the ortho-substituted one exhibits not only enhanced and accelerated AIE performance, but also improved 2PA properties. This research would provide a general approach to explore efficient molecules by the marriage of accelerated AIE and enhanced 2PA that could improve their performance in various areas.