The invention belongs to the technical field of using an electrochemical method for processing organic-polluted waste water, and in particular relates to a microwave electrochemical method for processing waste water and devices. A boron-mixed diamond membrane electrode which has stable work under microwave action is used as an anode material of electrochemical degradation processing of the invention. Devices comprise a thermostatic bath, a peristaltic pump, a flow meter, a reactor, a boron-mixed diamond membrane electrode (anode), a titanium electrode (cathode) and a microwave oven. The invention uses microwaves for promoting the mass transferring process of organic pollutants, activates the boron-mixed diamond membrane electrode, improves electrode activity and accelerates the velocity ofelectrochemical oxidizing reaction. Compared with that of the pure electrochemical oxidization, in the same time, the removal rate of 2,4-dichlorphenoxyacetic acid of the invention is increased by 152 percents. The method has simple operation, and has good processing effect on organic waste water, and wide application prospect and developing potential.