By using college students career decision-making self-efficacy scale table, achievement motivation scale table, we surveyed 812 students in the 5 colleges of Chongqing, and used parametric test, correlation analysis, regression analysis statistical methods to explore the relationship of self-efficacy and achievement-motivation. The results showed: the level of career decision-making self-efficacy is moderate. There are significant differences in gender, grade, major, native place, whether or not singleton, whether or not student leader, and whether or not a part-time reflecting the various characteristics of the decision-making self-efficacy. Post-secondary's vocational decision-making self-efficacy and its dimensions have significant positive correlation with the motivation to succeed, negative correlation with the motivation to avoid failure the motivation of pursuing success and synthesis motivation have a significant positive correlation only with self-programming efficacy.