A novel process was designed for synthesis of cyclohexanone oxime using ammonium chloride as nitrogen source. Various reaction parameters were optimized such as the amount of ammonium chloride, catalyst and H2O2, reaction temperature, reaction time. Under the suitable reaction conditions, nearly 100% of conversion of cyclohexanone and 100% selectivity of cyclohexanone oxime were obtained at ambient condition. The reaction mechanism was proposed by combining experiments with density functional theory calculations.