In this article, a new series of conjugated polymers based on a low-cost, easily accessible vat dye called Vat orange 1 or 2,9-dibromo-dibenzo[b,def]chrysene-7,14-dione have been prepared. This compound was made electron-donating by reducing and alkylating the ketone groups into alkoxy groups, allowing the introduction of solubilizing, branched alkyl chains at the 7 and 14 positions. Polymerization reactions using Suzuki–Miyaura coupling with 6,6′-isoindigo, 3,6-di-2-thienyl-pyrrolo[3,4-c]pyrrole-1,4-dione (DPP) and 4,7-dithieno-2,1,3-benzothiadiazole (TBT) yielded three donor–acceptor polymers with bandgap values ranging from 1.61 to 1.86 eV. Field-effect transistors (OFETs) and organic solar cells (OSCs) were fabricated and hole mobility values of up to 3.62 × 10⁻⁴ cm² V⁻¹ s⁻¹ and a maximum power conversion efficiency of 1.2% were measured, respectively.