Two new small molecules with a rigid planar naphtho[1,2-b:5,6-b′]dithiophene (NDT) unit were designed and synthesized. Solution processed bulk-hetereojunction organic solar cells based on blends of the small molecules and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) exhibited promising photovoltaic device performance with a maximum power conversion efficiency up to 2.20% under the illumination of AM 1.5G, 100 mW cm−2.