The invention discloses a preparation method of an MIL-100(Fe) packaged phosphotungstic heteropolyacid catalyst. The preparation method comprises the steps of: adding raw materials for synthesizing phosphotungstic heteropolyacid into a certain amount of deionized water based on certain proportion; subsequently adding a certain amount of an iron source, mixing and stirring, further adding a certain amount of an organic ligand, mixing, stirring, adding a certain amount of an acid solution, and mixing and stirring; mixing, stirring and reacting for 5-20 hours under normal pressure at 80-95 DEG C; and filtering the obtained solid, washing for 10-20 hours at 60-80 DEG C by using absolute ethyl alcohol, subsequently treating for 10-15 hours at 60-80 DEG C by using a 30-60mmol / L ammonium fluoride solution, sufficiently washing by using deionized water, and finally drying for 5-10 hours at 100-200 DEG C so as to obtain the MIL-100(Fe) packaged phosphotungstic heteropolyacid catalyst. The method is temperate in synthesis condition, low in synthesis energy consumption and high in catalyst synthesis yield.