During the past years, one of the most iconic metal–organic frameworks (MOFs), MOF-5, has been characterized as a semiconductor by theory and experiments. Here we employ the GW many-body perturbation theory in conjunction with the Bethe–Salpeter equation to compute the electronic structure and optical properties of this MOF. The GW calculations show that MOF-5 is a wide-band-gap insulator with a fundamental gap of ∼8 eV. The strong excitonic effects, arising from highly localized states and low screening, result in an optical gap of 4.5 eV and in an optical absorption spectrum in excellent agreement with experiments. The origin of the incorrect conclusion reported by past studies and the implication of this result are also discussed.