The third component in binary organic photovoltaics (OPV) plays a crucial role in finely adjusting light absorption, reducing energy loss, and optimizing the blend morphology. We introduce four A-π-D-π-A type small molecules as guest-donor materials, employing easily accessible starting materials. These molecules incorporate carbazole or bicarbazole as the core structure, along with pyran-4-ylidene-malononitrile or pyran-4-ylidene-indenedione derivatives as electron-accepting end groups. We explore the miscibility of guest donors with Y6 and analyze the energy loss in corresponding OPVs. Tapping mode atomic force microscopy and grazing incidence wide-angle X-ray (GIWAX) scattering analysis confirm that the twisted configuration of the guest donor CY-3 disperses effectively into the Y6 domain, promoting the formation of an alloy-like structure and maximizing the energy gap (Egap) of OPVs. CY-3 improves the molecular packing of Y6 in ternary blend and optimizes the blend morphology, leading to the minimum non-radiative energy recombination (ΔEnon-rad) and energy loss (Eloss) in the corresponding ternary OPV which exhibits an optimized Voc of (0.891 ± 0.006 V). The optimized blend morphology also, suppresses bimolecular and trap-assisted recombination, and improves charge collection. Ternary devices employing PM6/PY-IT, PM6/Y18, PM6/L8-BO, and PM6/BTP-eC9 demonstrate significant improvements in their Voc. Particularly remarkable is the attainment of the highest PCE of 17.18 % in the OPV based on PM6/BTP-eC9 with the incorporation of CY-3.