Three novel N-heteroacene molecules (SDNU-1, SDNU-2 and SDNU-3)b ased on tetraazachrysene units as cores have been designed, synthesized and fully characterized. Their photophysical, electrochemical and fluorescence properties were investigated, and they exhibited blue to green emission in the solid state. Interestingly, SDNU-2 exhibited high solid photoluminescence quantum efficiencies (75.3 %), which is the highest value of N-heteroacenes derivatives to date. Two-photon absorption studies have been conducted by using the open and close apertureZ -san tech-nique. SDNU-3 showed as ignificant enhancement in the two-photon absorption cross-section with magnitudes as high as about 700 GM (1 GM = 1 10 À50 cm 4 s/photon)w hen excited with 800 nm light, which is the largest value based on ah eteroacene system measured by using aZ -scan experiment so far.W ea ttribute the outcomet os ufficient electronic coupling between the strong charge transfer of quadrupolars ubstituents and the tetraazachrysenec ore. Our result would provide an ew guideline to design novel efficient two-photon materials based on N-heteroacene cores.