The relocation of chemical enterprises along the Yangtze River a necessary means of ecological protection in the Yangtze River Basin. Vulnerability assessment provides a new idea for the study of livelihood ability and compensation standard of employees after relocation. Based on the framework of "Exposure-Sensitivity-Adaptability" proposed by the Intergovernmental Panel on Climate Change (IPCC) and the survey data of 410 employees of relocation enterprises in the Hubei Province of the Yangtze River Basin, this study firstly constructs a livelihood vulnerability evaluation index system and evaluation model, and analyzes whether the employees of relocation enterprises have the ability to cope with the risk impact brought by the Yangtze River Ecological Restoration policy. Then, we use multiple linear regression model to explore the relationship between the group's exposure, sensitivity, adaptability and livelihood vulnerability. Finally, we design a new compensation standard calculation method for special groups from the perspective of social cost, to alleviate their livelihood vulnerability and provide a theoretical basis and decision support for the government and enterprises to formulate and implement relevant resettlement standards. The results show that: (1) employees of all ages show a certain degree of vulnerability in their livelihood; (2) there are differences in livelihood vulnerability between male and female employees; (3) compared with other positions, the livelihood vulnerability of producers is relatively high, and the vulnerability index is unevenly distributed and internally differentiated; (4) a low family burden ratio, high education, convenient living conditions and complex social network can effectively reduce the vulnerability of employees' livelihood; (5) the key obstacle factors affecting the sustainable livelihood of families are living convenience, adaptability to relocation, policy understanding, children's burden ratio, education, and annual income per capita; (6) the alternative opportunity cost method can be used as the basis to determine the compensation standard of the relocated employees, which can better reflect the compensation effect of the opportunity cost in the existing definition of international compensation mechanisms and realize the leap from concept to action.