Two anthracene-based star-shaped conjugated small molecules, 5′,5″-(9,10-bis((4-hexylphenyl)ethynyl)anthracene-2,6-diyl)bis(5-hexyl-2,2′-bithiophene), HBantHBT, and 5′,5″-(9,10-bis(phenylethynyl)anthracene-2,6-diyl)bis(5-hexyl-2,2′-bithiophene), BantHBT, are used as electron-cascade donor materials by incorporating them into organic photovoltaic cells prepared using a poly((5,5-E-alpha-((2-thienyl)methylene)-2-thiopheneacetonitrile)-alt-2,6-[(1,5-didecyloxy)naphthalene])) (PBTADN):[6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) blend. The small molecules penetrate the PBTADN:PC71BM blend layer to yield complementary absorption spectra through appropriate energy level alignment and optimal domain sizes for charge carrier transfer. A high short-circuit current (JSC) and fill factor (FF) are obtained using solar cells prepared with the ternary blend. The highest photovoltaic performance of the PBTADN:BantHBT:PC71BM blend solar cells is characterized by a JSC of 11.0 mA cm−2, an open circuit voltage (VOC) of 0.91 V, a FF of 56.4%, and a power conversion efficiency (PCE) of 5.6% under AM1.5G illumination (with a high intensity of 100 mW−2). The effects of the small molecules on the ternary blend are investigated by comparison with the traditional poly(3-hexylthiophene) (P3HT):[6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) system.