Two novel oxo-vanadium complexes of VO(HB(pz)3)(pzH)(SCN) (1) and VO(HB(3,5-Me2pz)3) (3,5-Me2pzH)(SCN)(SCNH)2 (2) with tris(pyrazolyl) hydroborate ligands were prepared by the reaction of VOSO4?nH2O, KSCN with Na(HB(pz)3), pyrazole, or Na(HB(3,5-Me2pz)3) and methyl-substituted pyrazole in the solution of MeOH, respectively. The complexes were characterized by element analysis, IR, and UV- vis spectra. In the mean time, the fluorescence spec-trum was studied too, and the result indicates that the luminescence of the complexes is related to the in-teraction between oxovanadium ion and tris(pyra- zolyl) hydroborate ligands. In addition, structures of oxovanadium complexes 1 and 2 were determined by X-ray diffraction. The electronic structures and the bonding characters of the two complexes were ana-lyzed with ab initio calculations. Two novel oxo-vanadium complexes of VO (HB (pz) 3) (pzH) (SCN) (1) and VO (2) with tris (pyrazolyl) hydroborate ligands were prepared by the reaction of VOSO4® nH2O, KSCN with Na (HB (pz) 3), pyrazole, or Na substituted pyrazole in the solution of MeOH, respectively. The complexes were characterized by element analysis, IR, and UV-vis spectra. In the mean time, the fluorescence spec-trum was studied too, and the results indicates that the luminescence of the complexes The additions structures of the oxovanadium complexes 1 and 2 were determined by X-ray diffraction. The electronic structures and the bonding characters of the two complexes were ana-lyzed with ab initio calculations.