The photophysical and electrochemical properties of four novel donor-accepter (D-A) conjugated oligomers a-d based on 3,4-ethylenedioxythiophene (EDOT) and electrondeficient heterocycle rings were investigated. The UV-vis absorption spectroscopy, fluorescence emission spectroscopy and cyclic voltammertry studies suggest that the oligomers are expected to provide enhanced charge-transporting properties for the development of efficient electroluminescent materials. Furthermore, the third-order nonlinear optical (NLO) measurements made by Z-scan technique indicate that they have good third-order NLO response and are desired materias for fabricating nonlinear photonic devices. In the solid state of these oligomers, a strong tendency of self-assembled structure was also revealed by X-ray diffraction (XRD) patterns in powder.