Objective: To systematically evaluate the application effect of a self-developed teaching case collection for emergency nursing courses and explore its value in enhancing students’ core clinical competencies. Methods: Based on the characteristics of nursing education and the training requirements for higher vocational students, a teaching case collection suitable for the nursing major was constructed. Students enrolled in the nursing major in Grade 2022 were selected as the control group (traditional teaching mode, n = 1081), and students in Grade 2023 were selected as the experimental group (case-based teaching mode, n = 1038). The control group received conventional theoretical and practical teaching, while the experimental group received case-based teaching using the case collection in addition to conventional teaching. Self-designed questionnaires were used to survey the control group, clinical instructors, and external review experts. Objective evaluations were conducted through theoretical tests and objective structured clinical examinations for both groups. The two groups were compared in terms of theoretical scores, practical skills, autonomous learning ability, and teaching satisfaction. Results: A teaching case collection containing 33 cases covering 10 symptoms (such as dyspnea, chest pain, and abdominal pain) was successfully constructed. The experimental group showed significantly better results than the control group in theoretical scores (86.54 ± 6.32 vs. 78.21 ± 7.85), practical scores (88.92 ± 5.14 vs. 81.45 ± 6.73), and total autonomous learning ability scores (85.37 ± 8.21 vs. 74.56 ± 9.03) (all P < 0.05). Additionally, 91.67% of students were satisfied with the case-based teaching mode, 95.83% believed case teaching improved clinical thinking ability, and 97.22% of instructors felt that the case collection enhanced lesson preparation efficiency and teaching effectiveness. Conclusion: The “Emergency Nursing Teaching Case Collection” fills the gap in systematic teaching cases for emergency nursing. Compared with traditional teaching, the case-based teaching mode more effectively improves students’ comprehensive competencies and has been widely recognized by both students and instructors, providing effective resource support for the reform of emergency nursing teaching.