This paper selects 69 coal mine rescue accidents from 1981 to 2011 in China, focusing on direct unsafe acts and high-frequency unsafe acts that lead to coal mine rescue accidents. Two conclusions can be drawn. The first conclusion is that there are five categories of direct unsafe acts that cause coal mine rescue accidents: not wearing respirators as required, not following the gas detection requirements, the poor abilities of the ambulance crew, technical measures not in place, and the violation of commanding. The first two has a larger proportion, as their sum is 57.97%, more than half. The second conclusion is that out of all relevant unsafe acts, nineteen categories of high-frequency unsafe acts are statistically significant, and 5 types are well-marked due to their higher frequency: not wearing respirators when rescuing, talking through respirator in the underground rescue process, not testing underground gas composition dynamically, not carrying a spare respirator, no pro-examination of the equipment. The analysis results can be used to educate employees and students.