A-π-D-π-A-based small molecules 6,6′-((thiophene-2,5-diylbis(ethyne-2,1-diyl))bis(thiophene-5,2-diyl))bis(2,5-bis(2-ethylhexyl)-3-(thiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione) (TDPP-T) and 6,6′-(((2,3-dihydrothieno[3,4-b][1,4]dioxine-5,7-diyl)bis(ethyne-2,1-diyl))bis(thiophene-5,2-diyl))bis(2,5-bis(2-ethylhexyl)-3-(thiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione) (TDPP-EDOT) have been designed and synthesized. The diketopyrrolopyrrole acts as an electron acceptor, while the thiophene or 3,4-ethylenedioxythiophene acts as an electron donor. The donor–acceptor groups are connected by an ethynyl bridge to further enhance the conjugation. The optoelectronics, electrochemical, and thermal properties have been investigated. Organic thin film transistor (OTFT) devices prepared from TDPP-T and TDPP-EDOT have shown p-type mobility. In as cast films, TDPP-T and TDPP-EDOT have shown a hole mobility of 5.44 × 10−6 cm2 V−1 s−1 and 4.13 × 10−6 cm2 V−1 s−1, respectively. The increase in the mobility of TDPP-T and TDPP-EDOT OTFT devices was observed after annealing at 150 °C, after which the mobilities were 3.11 × 10−4 cm2 V−1 s−1 and 2.63 × 10−4 cm2 V−1 s−1, respectively.