The separation between methane and nitrogen is an inevitable and important task in the Cl chemical technology and the utilization of methane from coalbed, yet it is considered to be one of the tough tasks in the field of separation. Pressure swing adsorption is a preferable technology if an adsorbent that allowing a large coefficient of separation for the CH4/N-2 system is available. The separation coefficients between CH4 and N-2 were obtained on analyzing the breakthrough curves measured experimentally with nine adsorbents. A technique of measuring the temperature-pulse was incorporated in the experiments, and the reliability of the result was improved. Superactivated carbon with large surface area and plenty of micropores was shown to have the largest separation coefficient and to be promising for the commercial utilization.