Recently, it was reported that OSCs based on non-fullerene acceptors have shown high photovoltaic performance with over 18% efficiency, being more than the power conversion efficiencies (PCEs) of 13% in OSCs based on fullerene. We considered theoretically the effects of fluorine atoms on the conversion efficiency of organic thin-film solar cells from the electronic analysis of donor/acceptor (D/A) complex interactions for NTz-Teh-FA and FNTz-Teh-FA using DFT. It was confirmed that it differs depending on the side-chain length, and it is necessary to consider the side-chain length. Because the longer the side-chain length, the lighter absorption and increased charge transfer. In the fluorinated acceptor, the polarity around the O atoms at both ends of the main chain was weakened, the twist angle of the molecular structure was reduced, and the light absorption at 600–700 nm was increased in the absorption spectrum. Therefore, it is considered that the fluorinated nonfullerene-type acceptor FNTz-Teh-FA, which has a long side chain, has the best light absorption and charge transfer. Excitation Energy Transfer (EET) calculations show that the Coulomb coupling contributes significantly. In addition, it was confirmed that the fluorinated complex had a higher EET. Therefore, it is considered that the charge separation efficiency is improved. Thus, it is considered that the short-circuit current density (JSC) is improved by improving the internal quantum efficiency (IQE), including the element of the charge separation efficiency.