The invention discloses a preparation method of aromatic diether dianhydride, which comprises the following steps: S1, feeding: adding a dihydroxyl
monomer, an alkaline compound, a
transition metal complex catalyst, an
organic solvent and a
water diversion agent into a reaction container, and continuously introducing
inert gas; s2, water separation: raising the temperature to separate out water in a
reaction system; s3, etherification reaction: adding a nitrophthalimide derivative, raising the temperature to carry out etherification reaction, filtering after the reaction is finished, and carrying out reduced pressure
distillation on filtrate to remove the
solvent, so as to obtain an etherified product; and S4, carrying out
hydrolysis ring opening, acidification and
dehydration ring formation on the etherification product to prepare the aromatic diether dianhydride. According to the preparation method of the aromatic diether dianhydride, the specific catalyst is introduced in the etherification reaction stage, a high-selectivity catalytic
system is formed, generation of by-products can be effectively inhibited, the yield and purity of target etherified products are remarkably improved, tedious steps of etherification and purification are avoided, the total preparation process is simplified, and the preparation method is suitable for industrial production.