Dithienopicenocarbazole (DTPC), as the inner core in the A-D-A configuration, has been recognized for its exceptionally small energy loss, narrow energy gap, and excellent power conversion efficiency. In this work, a series of six novel dithienopicenocarbazole-based molecules with wide absorption and remarkable opto-electrical properties, were designed as the new electron-donating materials for organic photovoltaic devices. (DI1-DI6) were derived by substituting end-capped moieties attached to the middle core (DTPC) with highly conjugated and electro withdrawing groups and insertion of π spacer between the donor part and the newly attached acceptor part. The findings demonstrated that the modified molecules had smaller excitation energies (Ex), a decreased energy gap (Eg), and have higher absorption (λmax) values in comparison to the DIR (reference structure). The greatest λmax (980 nm), smallest Ex (1.21 eV), and shortest Eg (1.63 eV) were all displayed by the DI4 molecule. In addition, due to its lowest RE value for the electron, DI4 might have best electron carrier ability among all. Furthermore, upon coupling each examined molecule with a PC61BM acceptor, the value of open circuit voltage (VOC) was computed. DI4 displayed the most suitable outcomes for the VOC (1.45 V), FF (0.91178) and normalized VOC (56.14). Therefore, all the altered structures, with special reference DI4, are strongly recommended to synthesize organic photovoltaic cells with exceptional optoelectronic and photovoltaic applications.