A series of new π-conjugated donor (thienyl – T) and acceptor (A) oligomers were prepared by Stille coupling reaction. The T–A oligomers consisting of thiophene/bithiophene as donors and 1,2,4-triazine as an acceptor were prepared to investigate their photophysical and electrochemical properties. These compounds were spectroscopically confirmed to be highly conjugated. These UV-vis data show that the number and position of the thiophene considerably affect the width of the HOMO–LUMO gap and the rigidity of the conjugated system. Compounds A2TA, A3TA, A4TA show photoluminescence in a range 466–543 nm.