Novel AIE-active, high T-g (up to 420 degrees C), and solution-processable wholly aromatic polyimides with triarylamine chromophores are synthesized and fabricated into highly effi cient photoluminescence (PL) nanofi bers by an electrospinning method. The PL intensity of polymer solutions is induced by aggregation in poor solvents, and they could be fabricated into solid fi lms with high PL quantum yields of up to 22%, demonstrating their aggregationinduced emission feature. Moreover, the electrospun nanofi bers have the highest PL quantum yield of 26% among aromatic polyimides, suggesting their great potential for high-performance optoelectronic applications.