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This study collected university students’ person-in-situation learning experiences four times daily over two weeks. We investigated the unique effect of perceived task difficulty on students’ four negative achievement emotions during learning events at both the within-person and between-person levels with Dynamic Structural Equation Modeling (DSEM). The interactive relationships between perceived competence and task difficulty with these negative emotions were explored. Results showed that negative emotions persisted across assessments, with task difficulty having a positive and significant effect on all negative emotions. Perceiving oneself as competent can effectively shield against the emotional challenges posed by difficult tasks. These findings enhance theoretical understanding of achievement emotions and offer practical implications for educators.