Vanadium(III) tris(metaphosphate), V(PO3)3, crystallizes in the monoclinic space group Ic with lattice parameters a = 10.615(2), b = 19.095(4), c = 9.432(1) Å, β = 97.94(1)° with Z = 12. The equivalent parameters in the standard space group Cc are a = 13.189(1), b = 19.095(4), c = 9.432(1) Å, and β = 127.15(1)°. The structure was refined by full-matrix least-squares to an R = 0.091 (Rω = 0.065) utilizing 2467 reflections with the atomic positions and their isotropic vibration amplitudes as parameters. The structure consists of infinite chains of PO4 tetrahedra sharing corners with each other and bridged by VO6 octahedra. All oxygen atoms are shared between just two cations. The average [Formula: see text] bond is 1.581 Å while the average of those shared with vanadium is 1.483 Å. The VO6 group is moderately distorted, with differences of less than 0.06 Å between the longest and shortest V—O bond lengths in any of the three distinct VO6 groups. The average V—O bond lengths for the three VO6 groups are 1.995, 1.991, and 1.987 Å. A marked superlattice effect based on a cell with b/3 is noted.