Liquid nitrogen freezing, which is an effective permeability enhancement technology, has been applied to the extraction of oil, shale gas, and coalbed methane (CBM). This study is aimed at revealing the effect of liquid nitrogen mass transfer on the temperature variation and pore structure evolution within coal. To achieve this aim, first, temperature measurement tests under the action of liquid nitrogen freezing were conducted on saturated and dried coal samples, respectively. Next, the coal samples were subjected to nuclear magnetic resonance and computer tomography tests before and after liquid nitrogen cold soaking to further explore the mechanism of coal temperature variation from a microscopic perspective. The results show that the action of liquid nitrogen mass transfer can accelerate coal temperature variation through coal pore structure and pore water phase change. The thermal stress and frost heave force generated by liquid nitrogen cold soaking exceed the tensile strength of the coal sample, which directly causes crack initiation, expansion, and connection. The mass transfer of liquid nitrogen has a significant promoting effect on pore development. This study provides the technical support necessary for the efficient exploitation of CBM resources and the improvement of CBM extraction rate.