Explore the influence mechanism of discrimination perception on higher vocational Students’ career exploration, it provides empirical evidence for promoting vocational college Students’ career exploration and career development. Using the questionnaire survey method, 893 higher vocational students from four higher vocational colleges in Jiangsu Province were investigated by using the Discrimination Perception Scale, the Core Self-Evaluation Scale (CSES), the Chinese version of the Acceptance and Action Questionnaire, the Chinese version of the Cognitive Fusion Questionnaire (CFQ) and the Career Exploration Scale (CES). The data were analyzed using SPSS26.0 and Amos23.0, and the results showed that discrimination perception was significantly negatively correlated with core self-evaluation, psychological flexibility and career exploration (r = −0.487, −0.497, −0.326, p < 0.01), core self-evaluation was significantly positively correlated with psychological flexibility and career exploration (r = 0.518, 0.352, p < 0.01), and psychological flexibility was significantly positively correlated with career exploration (r = 0.386, p < 0.01); Core self-evaluation and psychological flexibility mediated the effect between discrimination perception and career exploration with effect sizes of −0.054 and −0.061, respectively; Core self-evaluation and psychological flexibility mediated the chain effect between discrimination perception and career exploration of higher vocational students with effect sizes of −0.030. Therefore, discrimination perception not only directly influences career exploration of higher vocational students, but also indirectly influences career exploration of higher vocational students through the separate mediating effects of core self-evaluation and psychological flexibility and the chain mediating effects of core self-evaluation and psychological flexibility. Accordingly, the following suggestions are put forward, which should pay attention to the cultivation of core self-evaluation and psychological flexibility of higher vocational students, strengthen the teaching quality and improve the image of vocational colleges.