The structure of the vanadium(III) pyrophosphate LiVP2O7 was determined by single-crystal X-ray diffraction data. The title compound, which is isostructural with LiFeP2O7, crystallizes in the monoclinic space group P21 (No. 4) with a = 4.8048(6), b = 8.113(1), c = 6.9393(9) Å, β = 109.01(1)°, V = 255.75(7) Å3, Z = 2, and R = 0.022 for 607 unique reflections. The Li+ cations, which are located in the tunnels which are formed by corner-sharing VO6 octahedra and P2O7 groups, are each coordinated by four oxygen atoms in a geometry with the same general shape as that of SF4. The structure is discussed along with NaVP2O7 and CsVP2O7.