To simulate the types of coordination and solution structures of the active site of haloperoxidases, the interaction systems between diperoxovanadate complexes [OV(O2)2L]n-(n=1 or 3, L=oxalate or H2O) and a series of histidine-like ligands in solution have been studied by using 1D multinuclear (1H, 13C, and 51V) NMR, 2D diffusion ordered spectroscopy, and variable-temperature NMR in 0.15 mol/L NaCl ionic medium, representing the physiological conditions of human blood. Some direct NMR data are given for the first time. The reactivity among the histidinelike ligands is imidazole>2-methylimidazole>carnosine≈4-methylimidazole>histidine. Competitive coordinationinteractions result in a series of new peroxovanadate species [OV(O2)2L']- (L'=histidine-like ligands). When theligands are 4-methylimidazole, histidine, and carnosine, a pair of isomers have been observed, which are attributedto different types of coordination between vanadium atom and ligands. The results of density functional theorycalculations provided a reasonable explanation on the relative reactivity of the histidine-like ligands and the molarratios of isomers. Theoretical results signify the importance of the solvation effect for the reactivity and stability of the interaction systems.