A new layered vanadium selenite (2,2′-bipy)(H2O)V2SeO7 was prepared under hydrothermal conditions, and characterized by elemental analysis, IR and single crystal X-ray diffraction analysis.The compound crystallized in a triclinic system, P1 space group, a=0.842 93(2) nm,
b=0.928 67(3) nm, c=0.970 95(2) nm, α=97.037(2)°, β=110.806(2)°, γ=98.385 (2)°, V=0.690 3(3) nm3, Z=2, R1=0.022 5, wR2=0.069 3. The compound, (2,2′-bipy)(H2O)V2SeO7, has a layered structure constructed from eight membered rings
{V6Se2O25}, six membered rings {V4Se2O19}, four membered rings {V2Se2O13} that were arranged alternately, and then extended into three dimensional supramolecular array through π-π stacking contacts of 2,2′-bipyridine molecules. The fluorescence spectrum shows that the title compound exhibits blue emission in the solid state at room temperature.