We demonstrate a strategy for designing high-performance, ambipolar, acene-based field-effect transistor (FET) materials, which is based on the replacement of C−H moieties by nitrogen atoms in oligoacenes. By using this strategy, two organic semiconductors, 6,13-bis(triisopropylsilylethynyl)anthradipyridine (1) and 8,9,10,11-tetrafluoro-6,13-bis(triisopropylsilylethynyl)-1-azapentacene (3), were synthesized and their FET characteristics studied. Both materials exhibit high and balanced hole and electron mobilities, 1 having μh and μe of 0.11 and 0.15 cm2/V·s and 3 having μh and μe of 0.08 and 0.09 cm2/V·s, respectively. The successful demonstration of high and balanced ambipolar FET properties from nitrogen-containing oligoacenes opens up new opportunities for designing high-performance ambipolar organic semiconductors.