The distribution of vanadium and iron ionic species in the presence of picolinate ligand has been simulated at various conditions with different pH values and compositions in the decontamination waste solution. In spite of variations of metal concentration in the decontamination solution, the shape of distribution diagrams were not changed greatly at both high (the molar ratio of picolinate to vanadium is 6) and low (the molar ratio is 3) LOMI decontamination conditions. However, in the solution of low-picolinate condition the shape of the distribution diagram of iron(II)-picolinate complexes was changed significantly. This phenomenon is attributed to the shortage of relative amount of picolinate ligand to iron existed in the solution, and originated from the difference in stability constants for complexes formed between vanadium(III) and iron(II) species with picolinate ligand. The distribution diagrams obtained in this study can be applied very usefully to the prediction or understanding the reaction phenomena occurred at various conditions in the course of the LOMI waste treatments such as an ion exchange operation.