The aim of this paper is to analyze the deformation-failure degree and microstructure variations in coal under the cryogenic-freezing effect of liquid CO2. In this paper, X-ray CT scanning technology is adopted to measure the microscopic-morphological parameters of coal. Drawing support from the image processing and three-dimensional (3D) visualization functions of Avizo software, 3D spatial structure variation rules, as well as the deformation and permeability parameters, are quantitatively calculated. Under the effect of LCO2 cryogenic freezing, the macroscopic mechanical properties and deformation-failure degree of coal are thoroughly analyzed. The results show that fracture-scale parameters of treated coal are significantly increased, resulting in spatial structure parameters including the coal plug total volume (Vt), fracture network volume (V0), and proportion of fracture network (μ0) to increase by 17.11%, 56.57%, and 55.59%, respectively. A comparison analysis indicates that the coverage area of a single value function from the percolation theoretical model for treated coal plugs becomes larger, and its percolation curves are more intensive; the quantitative coal permeability coefficients are increased to more than 40% on average, which further proves that the permeability of coal by using LCO2 cryogenic freezing is significantly improved. Under the same uniaxial stress loading rate, the peak stress threshold value required by treated coal in the compaction and elastoplastic deformation stage is decreased. The corresponding output acoustic emission energy is apparently increased, owing to the increased brittleness of coal, and deformation failure of coal occurs more easily. Simultaneously, the fracture network and matrix surface of treated coal are more complex, and the corresponding fractal characteristic is obvious. It could be thus concluded that the coal plugs have deformation-failure changes under cryogenic freezing by using LCO2, increasing the proportion of coal microstructure and enhancing coal permeability. Therefore, the capability of gas migration through the coal microstructure becomes easier, which is favorable for coalbed methane recovery.