Purpose: Cognitive-motivational-relational theory (CMRT) emphasizes that cognitive appraisal components and core relational themes (in which the 6 separate appraisal judgments are brought together as 1) are the proximal determinants of athletes' emotions. This study aimed to explore appraisals associated with discrete emotions experienced by athletes during competition by adopting a naturalistic, qualitative video-assisted approach. Method: Thirty self-confrontation interviews were conducted with 11 national table-tennis players. Qualitative inductive and deductive content analyses were conducted on the participants' transcripts. Results: Content analyses suggested that primary and secondary appraisal components (goal relevance, goal congruence, ego involvement, blame or credit, coping potential, and future expectations) were associated with a range of positive and negative discrete emotions: self-, other-, and environmental-oriented anger, anxiety, discouragement, disappointment, disgust, joy, serenity, relief, hope, and pride. Hierarchical content analyses also provided some support for the concept of core relational themes. Conclusion: Findings of the present study are consistent with a CMRT approach and highlight that primary and secondary appraisals as well as core relational themes are associated with discrete emotions experienced by athletes while competing. Limitations and practical applications of this study are discussed.