First, hydrolyzing the Volvariella volvacea by mlti-enzyme complex hydrolysis technology, and then using microwave technology to hydrolyze, using orthogonal design method to determine the optimum extraction process of the Volvariella volvacea with microwave-enzymatic hydrolysis technology and the extract amount of α-Amino nitrogen as observing indexes and the optimum extraction process were as followed: hydrolysis time 120 min, hydrolysis temperature 55 ℃, edible fungus hydrolase No.1 to No. 2 dosage 1∶2(m∶m), initial pH 5.5, microwave power 800 W, microwave temperature 70 ℃, microwave time 10 min. The content of α-amino nitrogen in the orthogonal experiments of microwave-assisted extraction under mlti-enzyme was 0.181 g/100 g, and increased 83.0% higher than with the process under mlti-enzyme.