Copper vanadates have been proposed as promising photoanodes for water-splitting photoelectrochemical cells, but their performance has recently been shown to be severely limited. To understand this behavior, we study the electronic structure and the optical properties of beta-Cu(2)V(2)O(7 )both experimentally and computationally. The measured absorption spectrum shows an absorption peak at 1.5 eV followed by the onset of an apparent continuum at 2.26 eV, as generally found for this class of materials. We perform calculations within the framework of the QSG (W) over tilde method and the Bethe-Salpeter equation while including effects of magnetic ordering, nuclear quantum motion, and thermal vibrations. We demonstrate the occurrence of two kinds of excitons with high binding energies upon optical excitation in beta-Cu2V2O7, which account for the first absorption peak and the lower edge of the apparent continuum. The results are confirmed by photoluminescence measurements, where sub-band-gap emissions are found for both excitons. These results provide an explanation for the low photocatalytic efficiencies of copper vanadates, despite the favorable size of their optical band gaps.