New, neutral, meso-substituted tetrathia[22]annulene[2,1,2,1] aromatic macrocyclic architectures display p-type semiconductor behaviour and constitute efficacious molecular field-effect transistors with reproducible bulk-like carrier mobility (as high as 0.63 cm(2) V(-1) S(-1)) on highly crystalline thin films deposited on octadecyltrichlorosilane modified SiO(2).