We have measured the spectral photoresponse of Al/pentacene Schottky junction photodiodes and optical absorptionspectra of pentacene films thermally evaporated on glass. The photoelectric response exhibited the genuine highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) transition at 1.97 eV and interband absorption peaks at 2.3 and 2.5 eV. These peaks are also identified in the optical absorptionspectra, but they are dominated by additional strong exciton peaks at 1.82 and 2.1 eV. By comparing these complementary measurements, we determine the HOMO–LUMO gap energy of 1.97 eV and the fundamental exciton binding energy of 0.15 eV for thin solid pentacene.