The incorporation of an electron-accepting unit into π-conjugated systems is an important approach to modulate the physical properties of such molecules. To investigate the potential of tetrazolo[1,5-a]pyridine as an electron-accepting unit, a series of diarylated tetrazolo[1,5-a]pyridine derivatives was synthesized by treating the corresponding diarylated pyridine N-oxide with diphenylphosphoryl azide. Thermogravimetric analyses of these molecules indicated that they possessed good thermal stability. The bithiophene-substituted tetrazolo[1,5-a]pyridine compound showed stable transistor characteristics under repeated bias conditions.