To enhance desorption of coalbed methane and increase extraction efficiency, a technique using microwave irradiation is proposed. Methane desorption experiments without and with microwave irradiation were carried out in the laboratory using an experimental system developed to study methane desorption. The experimental results show that microwave irradiation causes the total quantity of methane desorbed to increase from 1.91 to 3.92 times larger than the quantity desorbed without MI. Two hour trials were performed, applying microwaves for 4, 8 or 16 min, equivalent to output energies of 192, 384 and 768 kJ. These results show that 1 kJ of microwave energy can cause methane desorption to increase by 0.0088 ml per gram of coal. Under successive microwave irradiations of 40 s, the desorption rate increases by a factor of 10.2. Kinetic analysis also found that microwave irradiation enhances the methane diffusion coefficient and decreases the attenuation coefficient. Regardless of which diffusion model is used to determine the diffusion coefficient, the quantity of gas desorbed increases as the microwave irradiation time increases. The pore and surface features of coal samples exposed to microwaves were determined by using mercury intrusion porosimetry and nitrogen adsorption and specimens were examined by scanning electron microscopy. Methane desorption evidently results from both the microwave thermal effect and structural damage to the coal. The results reported herein reveal the mechanisms that promote methane desorption by microwave irradiation and suggest a new field technique for extracting coalbed methane.