A hydrothermal reaction of NaVO3, Ce(NO3)3, H3BO3, 2,2′ bipyridine and water in a molar of 1∶2∶3∶2∶333 gives a yellow crystal [(C10H8N2)2VO2](H2BO3)·3H2O. It crystallizes in a triclinic with space group and unit cell parameters a=0.6643(1)nm, b=1.1794(2)nm, c=1.4822(3)nm, α=101.39(3)°, β=101.59(3)°, γ=97.15(3)°, Z=2, Dc=1.542g·cm-3, μ=0.508mm-1, F(000)=528, R1=0.0736, wR2=0.1998,Goof=1.071. X ray crystallographic study showed that the VN4O2 octahedron unit is distorted, in which the V1 atom is coordinated by two terminal O1 and O2 atoms, and N1, N2, N3 and N4 atoms from two 2,2′ bipy ligands. The hydrogen bonding are observed between 2,2′ bipy and adjacent terminal oxygen atom. It is noteworthy that π πstacking interaction between adjacent 2,2′ bipy groups plays an significant role in stabilization of the structure of crystal. CCDC: 194327.