The excited states of a symmetric D-pi-D structure two-photon excited fluorescence material 1,4-di (4'N-,N-diphenylaminostyryl) benzene (DPA-DSB) have been investigated by spectroscopic experiments and quantum chemical calculations. The solvent polarity dependent fluorescence properties indicate that upon photoexcitation, a radiative intramolecular charge-transfer (ICT) state is formed resulting from the ICT process. The molecular structure does not have large change during the ICT process, which is confirmed by the quantum chemical calculations performed by GAUSSIAN 03 software. The planar structure of the fluorescent ICT state results in the high fluorescence quantum yield which is important in the two-photon excited fluorescence application. (C) 2010 Elsevier B.V. All rights reserved.