Abstract: The importance of plutonium is only second to uranium in nuclear industry and its recovery had been researched extensively. The reduction of Pu(Ⅳ) by hydroxylamine and its derivatives is one of the main research directions. In this paper, the 3D structures of hydroxylamine and its derivatives were optimized and their energies were calculated by density functional theory(DFT) with B3LYP functional and 6-311+G(3d, 3p) basis set. The physicochemical parameters such as hydrophobic parameter, which could describe the structures were generated by HyperChem. The relationship between the halfreaction times and their physicochemical parameters was analyzed. Finally, the quantitative structure-activity relationships(QSAR) equation with a good correlation was obtained. The results show that the reaction relationship between the structure of hydroxylamine and its derivatives and Pu(Ⅳ) can be represented by QSAR equations. The total energy of molecular is a major factor affecting the reduction rate, and it is negatively correlated with the reaction rate.