;A set of novel unsymmetrically substituted and multi-branched chromophores containing pyridine and quinoxaline heterocyclic rings has been synthesized via Chichibabin pyridine synthesis and condensation. The results from linear optical property measurements show that these chromophores possess strong solvent effect on their fluorescence emission and lifetime behaviors. These model compounds also exhibit strong and broadly-dispersed two-photon absorptivities in the near infrared (NIR) within the spectral range of 680nm-1080nm. It is demonstrated that chromophores with more electron-donors and extended π-conjugation would exhibit stronger nonlinear absorptivities. It is also revealed that these 2,4,6-triaryl pyridine–based chromophores do not possess good coplanarity, which leads to limited π-electron delocalization and may hamper the molecular two-photon absorption.