New light is shed on the previously known perovskite material, Cs2Au2I6, as a potential active material for high-efficiency thin-film Pb-free photovoltaic cells. First-principles calculations demonstrate that Cs2Au2I6 has an optimal band gap that is close to the Shockley-Queisser value. The band gap size is governed by intermediate band formation. Charge disproportionation on Au makes Cs2Au2I6 a double-perovskite material, although it is stoichiometrically a single perovskite. In contrast to most previously discussed double perovskites, Cs2Au2I6 has a direct-band-gap feature, and optical simulation predicts that a very thin layer of active material is sufficient to achieve a high photoconversion efficiency using a polycrystalline film layer. The already confirmed synthesizability of this material, coupled with the state-of-the-art multiscale simulations connecting from the material to the device, strongly suggests that Cs2Au2I6 will serve as the active material in highly efficient, nontoxic, and thin-film perovskite solar cells in the very near future.