The crystal structure of the low-temperature form of magnesium pyrovanadate (Mg2V2O7) has been determined from synchrotron X-ray powder diffraction data using Rietveld refinement. α-Mg2V2O7 is isostructural with Co2V2O7 and Ni2V2O7. The Mg2+ ions are octahedrally coordinated to oxygen atoms in a distorted arrangement while the pyrovanadate anion has an approximately eclipsed conformation of non-bridging oxygen atoms. The 51V MAS NMR spectra of the central and satellite transitions for the two distinct 51V sites in α-Mg2V2O7 allow determination of the magnitudes and relative orientations of the 51V quadrupole coupling and chemical shift tensors. The crystal structure data are used to calculate the principal elements of the 51V electric field gradient tensors employing the point-monopole approach. A good correlation between these elements and the experimental 51V quadrupole tensor elements is observed, which allows assignment of the quadrupole coupling constants of CQ = 4.80 MHz and CQ = 3.33 MHz to the crystallographic V(1) and V(2) sites, respectively.