A method for preparing hydroxylamine is provided that includes the steps of (i) pretreating an acidic buffer solution; and (ii) reducing nitrate ions in the acidic buffer solution with hydrogen to give hydroxylamine in the presence of catalysts, wherein the pretreatment is performed by adding a precipitant represented by formula (I) to the acidic buffer solution, [(A)aM(CN)6.xH2O]  (I) allowing the metal impurities in the acidic buffer solution to react with the precipitant to form metal complex, and then to remove the metal complex. The metal complex is formed and separated by pretreating the acidic buffer solution with a specific precipitant without adjusting pH and changing the composition of the acidic buffer solution prior to hydroxylamine synthesis, thus enhancing the selectivity of the hydroxylamine production.