4,4′-ether dinaphthalene 1,1′,8,8′-tetracarboxylic dianhydride was synthesized by using acenaphthene as raw material through Nitration, reduction, Bucherer reverse reaction, etherification and oxidation. The conditions of phenol self-coupling etherification under microwave irradiation were investigated. Results showed that the best conditions under microwave irradiation were the power of 600 W, the temperature of 150 ℃, and the reaction time of only 2 h , with the yield of 57.8%.