Coal mine accidents often lead to economic losses and casualties. Establishing a coal mine emergency reserve can help rescue materials reach the accidental coal mine site more quickly, so the site selection of the emergency reserve is crucial. This paper proposes a siting method based on multi-objective decision-making, taking the shortest total emergency rescue time, the largest total attraction between the reserve and the coal mine, and the lowest total cost of siting as the optimization objectives, and constructing a multi-objective siting planning model. The second-generation non-dominated sorting genetic algorithm (NSGA-II), combined with the entropy value method (EWM) and the method of approximating the ideal solution sorting (TOPSIS), is used to select the optimal site selection scheme. Taking Liaoning Province as an example, the results of the study show that (1) Program No. 47 has the highest ranking among all the programs. (2) The sensitivity analysis shows that the service radius of the reserve depot is more sensitive to the optimization results, which verifies the rationality of the scheme. (3) Compared with the current stage reserve depot system in Liaoning Province, the total cost is saved by 23.03% and the total time is saved by 26.98%. Therefore, this method is of some reference significance for the selection of a site for an emergency material reserve depot.