A facile synthesis of air-stable anthra[1,2-b:4,3-b':5,6-b'':8,7-b''']tetrathiophene derivatives 1a and 1b has been developed for applications in organic thin film transistors. Both molecules tend to self-associate through pi-pi stacking in solution and in different films. The hole mobility of 0.012 cm2 V(-1) s(-1) is obtained from 1a due to morphology changes in films from less ordered to highly ordered structures after thermal annealing. Good performance remained persistent over a period of 14 days, indicating the high stability of such transistors.