A series of nitrogen-bridged donor–acceptor–donor (D–A–D) type molecules, 1–3, was synthesized using thiophene/selenophene as donors and benzothiadiazole(BTD)/benzoselenadiazole(BSeD) as acceptors. Compound 1 contains a sulfur (S) atom in both the donor and acceptor which was changed to selenium (Se) in 2 for the donor and in 3 for the acceptor. The juggling of S/Se atom(s) in the donor or acceptor unit helps in modulating the structural, photophysical, and electrochemical properties of the resulting compounds. As revealed from crystal structures, compounds 2 and 3 dimerize via S⋯N and Se⋯N interactions, respectively. Compounds 1–3 were successfully polymerized by electrochemical polymerization and the resulting polymers were studied electrochemically. Compounds 1–3 show high fluorescence quantum yields, positive solvatochromism, and high stokes shifts.