A hyperbranched poly(aroylarylene) containing triphenylamine (TPA) moiety (hb-P1) is synthesized by metal-free polycyclotrimerization of N,N-bis(4-ethynylcarbonylphenyl)aniline (1) in a high yield (86%) with a perfect 1,3,5-regioregularity. The polymer is soluble in common organic solvents such as THF and chloroform and is thermally stable, losing 5% of its weight when heated to a temperature as high as similar to 450 degrees C. The polymer is fluorescent and solvatochromic, whose emission color changes from similar to 455 nm (blue) in toluene to 549 nm (yellow) in DMF. The polymer exhibits a large two-photon absorption cross-section due to the intramolecular charge transfer between its electron-donating TPA and electron-withdrawing 1,3,5-tricarbonylbenzene groups.