Ambipolar transistor properties have been observed in various small-molecule materials. Since a small energy gap is necessary, many types of molecular designs including extended π-skeletons as well as the incorporation of donor and acceptor units have been attempted. In addition to the energy levels, an inert passivation layer is important to observe ambipolar transistor properties. Ambipolar transport has been observed in extraordinary π-electron systems such as antiaromatic compounds, biradicals, radicals, metal complexes, and hydrogen-bonded materials. Several donor/acceptor cocrystals show ambipolar transport as well.