In the paper, a new A-pi-D-pi-A small molecule with alkoxyphenyl substituted naphtho[1,2-b:5,6-b']difuran (NDFP) as the central building block, named as NDFP-CNCOO which was synthesized and firstly used as donor materials in organic solar cells (OSCs). After thermal annealing (TA), the blend of NDFP-CNCOO/PC71BM (1:1, w/w) exhibited a high electron mobility of 1.84 x 10(-4) cm(2) V-1 s(-1). Using a structure of ITO/PEDOT:PSS/NDFP-CNCOO: PC71BM/Al, the device delivered a moderate power conversion efficiency (PCE) of 4.60% and a high fill factor (FF) of 57% with TA at 110 degrees C. The investigations show that NDFP-CNCOO could be a promising building block in OSCs via rational molecular structure design and device optimizations.