To address the increasing demand of efficient photovoltaic compounds for modern hi-tech applications, efforts have been made herein to design and explore triazatruxene-based novel donor materials with greater efficiencies. Five new molecules, namely M1–M5, were designed by structural modification of acceptor moiety (rhodanine-3-acetic acid) of well known experimentally synthesized JY05 dye (reference R), and their optoelectronic properties are evaluated to be used as donor molecules in organic solar cells. In these molecules M1–M5, triazatruxene acts as a donor unit and benzene spaced different end-capped moieties including 2-(4-(dicyanomethylene)-2-thioxothiazolidin-3-yl)acetic acid (A1), (E)-2-(4-(1-cyano-2-methoxy-2-oxoethylidene)-2-thioxothiazolidin-3-yl)acetic acid (A2), (Z)-2-(3′-ethyl-4′-oxo-2,2′-dithioxo-3′,4′-dihydro-2′H,5H-[4,5′-bithiazolylidene]-3(2H)-yl)acetic acid (A3), (Z)-2-(4′-(dicyano-methylene)-3′-ethyl-2,2′-dithioxo-3′,4′-dihydro-2′H,5H-[4,5′-bithiazol-ylidene]-3(2H)-yl)acetic acid (A4) and 2-((4Z,4′E)-4′-(1-cyano-2-methoxy-2-oxoethylidene)-3′-ethyl-2,2′-dithioxo-3′,4′-dihydro-2′H,5H-[4,5′-bithiazolylidene]-3(2H)-yl)acetic acid (A5) respectively, as acceptor units. The electronic, photophysical and photovoltaic properties of the designed molecules M1–M5 have been compared with reference molecule R. All designed molecules exhibit reduced energy gap in the region of 1.464–2.008 eV as compared to reference molecule (2.509 eV). Frontier molecular orbital (FMO) surfaces confirm the transfer of charge from donor to acceptor units. All designed molecules M1–M5 exhibited an absorption spectrum in the visible region and they were broader as compared to that of reference R. Especially, M5 with highest λ_max value 649.26 nm and lowest transition energy value 1.90 eV was accredited to the strong electron withdrawing end-capped acceptor moiety A5. The highest value of open circuit voltage (V_oc) 1.02 eV with respect to HOMO_donor–LUMO_BTP-4Cl was shown by M5 among all investigated molecules which was 0.15 V larger than reference molecule R. The designed molecule M5 is proven to be the best candidate for both electron and hole transport mobilities due to its smallest λ_e (0.0212 eV) and λ_h (0.0062 eV) values among all studied molecules.