We have designed and synthesized a new donor/acceptor-type tetracene derivative by the introduction of dicarboxylic imide and disulfide groups as electron-withdrawing and -donating units, respectively. The prepared compounds, tetracene dicarboxylic imide (TI) and its disulfide (TIDS) have high chemical and electrochemical stability as well as long-wavelength absorptions of up to 886 nm in the thin films. The crystal packing structure of TIDS molecules features face-to-face π-stacking, derived from dipole–dipole interactions. Notably, TIDS exhibited ambipolar properties of both electron-donating and -accepting natures in p–n and p–i–n heterojunction organic thin-film photovoltaic devices. Accordingly, TI and TIDS are expected to be promising compounds for designing new organic semiconductors.