Production of pure hydrogen from methane by a low temperature plasma process coupled with catalytic reaction was investigated. In low temperature plasma, methane molecules were converted to thin solid films and hydrogen. The conversion of methane and the hydrogen yield depended on the flow rate of methane and the discharge power for the low temperature plasma process. They increased as the flow rate decreased and the discharge power increased. A conversion as high as 87.4% and hydrogen yield as high as 67% could be obtained, but the purity of the hydrogen was less than 90%. The purity could be increased to 100% by coupling the low temperature plasma process with a catalytic reaction using a plasma-catalyst hybrid system.