Two donor-acceptor alternating copolymers based on electron-rich triarylamine, di(1-(6-(2-ethylhexyl)) naphthyl)phenylamine (DNPA), and electron-deficient benzothiadiazole and benzoselenadiazole derivatives were designed and synthesized via Suzuki coupling reaction. The resulting triarylamine-based alternating copolymers PDNPADTBT and PDNPADTBS showed good solubility in common organic solvents and good thermal stability. The optical band gaps determined from the onset absorption were 1.93 and 1.81 eV, respectively. By introducing the naphthalene ring into the triarylamine, copolymers had relatively deep HOMO energy levels of -5.48 and -5.45 eV, which led to a high open circuit voltage (V-oc) and good air stability for photovoltaic application. Bulk heterojunction solar cells were fabricated with a structure of ITO/PEDOT-PSS/copolymers-PC70BM/LiF/Al by blending the copolymer with PC70BM. Both blend systems showed remarkably high V-oc near 0.9 V, and the highest performance of 2.2% was obtained from PDNPADTBT, with V-oc = 0.88 V, J(sc) = 7.4 mA/cm(2), and a fill factor of 34.4% under AM 1.5 G.