Four asymmetric bis-branched triphenylamine-cored compounds with different electron-withdrawing groups have been synthesized and their optical properties have been systematically investigated. The two-photon absorption cross-section (sigma(2PA))values were measured by two-photon excited fluorescence which revealed that the four compounds possessed large sigma(2pA) values from 2011 to 4173 GM in the near infrared region. Theoretical calculations revealed that the compounds were all provided with interesting intramolecular charge transfer generated from one branch to the other which contributed to the large sigma(2PA) values. Cytotoxicity tests indicated that all these compounds had good biocompatibility for living cells, both one- and two-photon fluorescence microscopy studies showed the potential application of the four new compounds in cell imaging due to the large sigma(2pA) and appropriate biocompatibility. (C) 2016 Published by Elsevier Ltd.