We investigate the correlation of the number of thiophene units with the structural order and carrier mobility of the films through studies on thin-film transistors (TFTs) based on alpha-quinquethiophene (5T), alpha-sexithiophene (6T), and alpha-septithiophene (7T). The X-ray diffraction (XRD) data of the nT films deposited at low substrate temperatures present obviously different structural orders depending on the parity of the number of thiophene units. Although even-numbered nT films present well-ordered structures and large carrier mobilities, odd-numbered nT films present two different crystalline polymorphs and vastly low carrier mobilities reflecting the coexistence of two crystalline polymorphs. However, the XRD data of both even- and odd-numbered nT films deposited at high substrate temperatures indicate that the nT molecules form single well-ordered structures. Those ordered TFTs exhibit large carrier mobilities accompanying an increase in the number of thiophene units, 0.05, 0.08, and 0.13 cm(2) V-1 s(-1) for 5T, 6T, and 7T, respectively. The parity of the number of thiophene units affects the structural order intrinsically in grown thin films, and affects carrier mobilities extrinsically in their TFTs.