A new amorphous semiconducting polymer containing dodecylthiophene rings and a rigid thieno[3,2-b]thiophene ring, poly(2,5-bis(3'-dodecyl-2,2'-bithiophen-5-yl)thieno[3,2-b]thiophene) (NAP), was synthesized via a microwave-assisted Stille coupling reaction. The presence of the flexible unsubstituted thiophene ring units next to the rigid fused thiophene ring caused NAP to have an amorphous structure. This structure was confirmed by XRD. AFM, and computational calculations. In particular, the out-of-plane XRD patterns of NAP thin films exhibited no reflection peaks before or after the annealing process, indicating that the films had amorphous microstructures. In addition, AFM images of the NAP thin Films showed amorphous surface morphologies with very small root-mean-square (rms) surface roughnesses of 0.3-0.5 nm, independent of surface treatment or heat treatment. Computational calculations performed to investigate the preferred conformation of the polymer confirmed the amorphous characteristics of the NAP structure. On the basis of these findings, we propose how an amorphous NAP semiconductor can maintain high carrier mobility. A NAP-based TFT device exhibited a very high carrier mobility of 0.02 cm(2) V(-1) s(-1) with an on/off ratio of I x 105 and a very small threshold voltage of -2.0 V. This carrier mobility is the highest yet reported for TFTs based on amorphous semiconductors. Thus, the present findings suggest that an amorphous semiconductor layer comprised of NAP would be suitable for use in high-performance organic TFTs fabricated via simple processes in which neither surface treatment nor heat treatment is necessary.