Background: University students with vocational qualifications encounter more severe cultural, academic, and self-evaluated challenges in the transitional process than their peers with an academic pathway. This study investigated the predictive effect of cultural intelligence (CI), imposter syndrome (IS), and academic resilience (AR) on school belonging (SB) and their interplay mechanism from a positive and negative perspective. Method: We recruited 326 Chinese university students with a vocational route as the research subjects and designed a parallel mediation model to assess the hypothesized construct. Result: The participants had scores above the median in CI, AR, and SB, but they also obtained scores exceeding the median in moderate IS. CI positively and significantly predicted SB both directly and indirectly through AR, while IS negatively and significantly predicted AR. AR both partly mediated the effect of CI on SB and entirely mediated the impact of IS on SB. Conclusion: CI was the most crucial factor impacting SB, followed by AR and IS among Chinese university students with a vocational education and training (VET) pathway. Strategic interventions should be adopted to enhance their abilities to cope with diverse cultures, promote their resilience in facing academic difficulties, boost their self-achievement, and foster their sense of SB.