Methane desorption characteristics of coal under definite water pressure comprises a complex two-phase flow process. A series of mercury intrusion porosimetry (MIP) and desorption experiments at different water injection pressures are reported in this study. Three lumpy coal samples were used in desorption experiments at three different water injection pressures and at natural desorption for comparison. Samples comprising two ranks of coal were used for MIP measurements including the distribution of porosity and pore sizes. The results of this study enable the establishment of a new model that encompasses a critical theoretical pore size that is most effective for water injection into coalbeds and that can be related to water injection pressure, the length of residual water, and gas adsorption capacity. Data show that the use of different water injection pressures leads to different gas desorption capacities as well as variable time effects and degree of gas desorption. Critical pore size is therefore proposed as a new parameter that can be employed to describe high pressure water effects in the context of gas desorption and can be calculated using pore size and the volume distribution law, as well as via the moisture ratio that remains after experiments and the permanent desorption percentage.