The pore structure distribution of coal affects the permeability of coal, and determines the flow and occurrence state of coalbed methane and other fluids in coal. This paper carries out a number of nuclear magnetic resonance (NMR) tests on coal samples with different coal qualities treated by liquid nitrogen cold soaking, and studies the influence law of liquid nitrogen soaking on coal pore structures. It is found that the liquid nitrogen makes the T2 spectral peak shift to the right, and the anthracite changes from interval T2 spectrum to type T2. It indicates that liquid nitrogen cold soaking in the transformation of pore size to large size improves the pore connectivity and leads to more pore structures. With an increase in times of liquid nitrogen cold soaking, the size and number of coal pore structures gradually increase, and the increasing size is in the order of anthracite > bituminous > lignite. There is a positive correlation between the peak area and the times of liquid nitrogen cold soaking. The porosity and permeability of each coal sample increase with the times of liquid nitrogen cold soaking. From the MRI images of coal samples, it can be found that the liquid nitrogen cold soaking makes the microcracks extend and form a crack network with other cracks, thereby causing macroscopic damage. The research results are helpful to further reveal the microscopic mechanism of liquid nitrogen cold soaking on coal damage.