At present, civil servant positions have become the main employment target of many college students in China, and there is a deep motivation behind this phenomenon. This research conducted an empirical study on college students in 2022 with 566 valid data by using the convenience sampling method. The occupational values scale, political efficacy scale, and the willingness to apply for civil servants scale were used. Descriptive statistical analysis, correlation analysis, and common method deviation were performed by SPSS 26.0 to test the reliability of each scale and the discriminant validity of variables. In addition, the structural equation model and bias-corrected bootstrap were used to explore the influence of occupational values on college students’ willingness to apply for civil servants and analyze the mediating role of political efficacy. The results show that: (1) The dimensions of career stability, prestige value, and public service motivation of occupational values have significant positive impacts on college students’ willingness to apply for civil servants, among which public service motivation has the most significant impact. (2) Occupational values have significant positive impacts on college students’ political efficacy. (3) Political efficacy has a significant positive impact on the college students’ willingness to apply for civil servants. (4) Political efficacy plays a partial mediating role in the transmission path of occupational values and willingness to apply for civil servants. These findings further clarify the logical relationship between occupational values and civil servants’ willingness, providing a theoretical basis and practical reference for college educators to implement college students’ career education.