Functionalized quinolines with a D/A–A–D architecture were designed and analyzed as active layers for organic field-effect transistors. The electronic absorption, fluorescence emission, and electrochemical behavior of these materials were studied. Furthermore, the influence of various substituents on the transistor performance was investigated by fabricating their BGTC-OFET devices using the spin-coating technique. By employing pre- and post-annealing techniques, dense polycrystalline films with uniform surface coverage were obtained. All the new compounds exhibited p-channel transistor behavior. Compounds with the methoxyphenyl terminal functionalized with a D–A–D architecture exhibited the best p-channel transistor characteristics with a hole mobility of 0.0032 cm² V⁻¹ s⁻¹. The good charge carrier mobilities are supported by an electron-donating methoxy group as the end-group with high HOMO and LUMO energy levels, extensive π-conjugation, pi–pi stacking, and more efficient self-assembly.