A series of nine (9) donor-acceptor-donor (DAD) π-conjugated small molecules were synthesized via palladium catalyzed Stille aromatic cross-coupling reactions by the combination of six (6) heterocycle building blocks (thiophene, furan, thiazole, 2,1,3-benzothiadiazole, 2,1,3-pyridinothiadiazole, thienothiadiazole) acting as electron donating (thiazole, furan, thiophene) and electron deficient (benzothiadiazole, pyridinethiadiazole, thienothiadiazole) units. These model compounds enable determining the correspondence between the theoretical and experimental optical and electrochemical properties for the first time, via Density Functional Theory (DFT), time-dependent DFT, UV-Vis spectroscopy, and cyclic voltammetry, accordingly. The obtained theoretical models can be utilized for the design and synthesis of new DAD structures with precise optical bandgaps, absorption maxima, and energy levels suitable for different optoelectronic applications.