Significant changes to the new National College Entrance Examination (NCEE) and the implementation of the “Double First-Class” (DFC) initiative in China are coincidentally in the national spotlight and fall within the same policy window. However, few studies have investigated the effects of the new NCEE on the quality of students in DFC universities. By leveraging the 2018-2022 college admission data from Shandong Province, these effects are examined via the interrupted time-series technique. Weighted rankings for liberal arts and science disciplines and the admission ranking coefficient are adopted to ensure comparability before and after the reform. The findings reveal that after the reform, the quality of students in both world-class universities and first-class discipline universities improved, with greater improvements seen in world-class universities. Focusing on urban differences, the quality of students in DFC universities located in second-tier cities is found to have experienced a higher increase as compared with students in the first-tier and new first-tier cities. In addition, the reform has had different impacts on the quality of students in different majors. Furthermore, when selecting postsecondary institutions, high-scoring students prioritize the quality of universities and majors over urban factors. Finally, the implications of the new NCEE in relation to a sustainable development of DFC universities for research, policy, and practice are further discussed.