A new layered vanadium phosphate {[(phen)(VO)-O-IV](2)((V2O5)-O-V)(HPO4)}(n) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, and single-crystal X-ray diffraction. This compound crystallized in the monoclinic space group P2/c with a = 9.979(2) Angstrom, b = 9.886(2) Angstrom, c = 15.298(3) Angstrom, beta = 102.86(3)degrees, V = 1471.3(5) Angstrom(3), and Z = 4. In the structure of this compound, two nitrogen atoms of 1,10-phen are directly coordinated to the vanadium skeleton. Interestingly, the crystal structure consists of two types of chiral layers, one left-handed and the other right-handed, which lead to a racemic solid-state compound. In each layer, there coexist three distinct rings, described as a 8-membered ring {(V2P2O4)-P-oct}, 12-membered ring {(V2V2P2O6)-V-oct-P-tet}, and 16-membered ring {(V2V4P2O8)-V-ocl-P-tet}.