A largely pi-expanded thienoacene molecule, dinaphtho[2,3-d:2',3'-d']anthra[1,2-6:5,6-b']dithiophene (DNADT) has been successfully synthesized and characterized. Its fabricated OFET device exhibited the maximum hole mobility of up to 8.5 x 10(-2) cm(2) V-1 s(-1) which is three times higher than that of our previously reported nine-ring annulated compound, BBTADT. A detailed solid-state structure of DNADT by GIWAXS and AFM analyses have also been investigated.