Methane content in coal seam is an essential parameter for the assessment of coalbed gas reserves and is a threat to underground coal mining activities. Compared with the adsorption-isotherm-based indirect method, the direct method by sampling methane-bearing coal seams is apparently more accurate for predicting coalbed methane content. However, the traditional sampling method by using an opened sample tube or collecting drill cuttings with air drilling operation would lead to serious loss of coalbed methane in the sampling process. The pressurized sampling method by employing mechanical-valve-based pressure corer is expected to reduce the loss of coalbed methane, whereas it usually results in failure due to the wear of the mechanical valve. Sampling of methane-bearing coal seams by freezing was proposed in this study, and the coalbed gas desorption characteristics under freezing temperature were studied to verify the feasibility of this method. Results show that low temperature does not only improve the adsorption velocity of the coalbed gas, but also extend the adsorption process and increase the total adsorbed gas. The total adsorbed methane gas increased linearly with decreasing temperature, which was considered to be attributed to the decreased Gibbs free energy and molecular average free path of the coalbed gas molecular caused by low temperature. In contrast, the desorption velocity and total desorbed gas are significantly deceased under lower temperatures. The process of desorption can be divided into three phases. Desorption velocity decreases linearly at the first phase, and then, it shows a slow decreases at the second phase. Finally, the velocity of desorption levels off to a constant value at the third phase. The desorbed coalbed gas shows a parabolic relation to temperature at each phase, and it increases with increasing temperature at the first phase, and then, it poses a declining trend with increasing temperature at the rest phases. The experimental results show that decreasing the system temperature can restrain desorption of coalbed methane effectively, and it is proven to be a feasible way of sampling methane-bearing coal seams.