A simple and efficient approach for preparation of hydroxylamine sulfate from the hydrolysis reaction of cyclohexanone oxime in the presence of sulfuric acid has been developed in this work. The effects of the molar ratio of cyclohexanone oxime to sulfuric acid, the concentration of reactants, the reaction temperature, the reaction time and the extraction solvents on the hydrolysis reaction were investigated. The results indicated the conversion of cyclohexanone oxime was over 30% with excellent selectivity of cyclohexanone and hydroxylamine sulfate under the optimal reaction conditions. Furthermore, the enthalpy change, entropy change, Gibbs free energy change and thermodynamic equilibrium constant of the hydrolysis reaction were determined in present work. This reaction is an endothermic reaction and higher temperature is favorable for the synthesis of hydroxylamine sulfate. This new preparation method is simple, rapid, efficient and economical. Maybe this work can serve as a direction for preparation of other hydroxylamine salts by such hydrolysis reaction. (C) 2015 Elsevier B.V. All rights reserved.