With the aim of upgrading the power conversion efficiency of organic solar cells (OSCs), five novel non-fullerene, A2−D−A1−D−A2-type small molecules were designed that are derivatives of a recently synthesized molecule, DF-PCIC, reported for its efficient properties in all-small-molecule OSCs (ASM-OSCs). Optoelectronic properties of the designed molecules were theoretically computed with a selected MPW1PW91 functional accompanied by the 6-31G(d,p) basis set of density functional theory (DFT), and excited-state calculations were performed through the time-dependent self-consistent field. geometricGeometric variables such as density of state (DOS), electrostatic potential (ESP), transition density matrix (TDM), binding energy (Eb), dipole moment (μ), reorganization energy (RE), and device performance (VOC) hadhave been enumerated and compared with reference to DF-PCIC.