<p>Thriving at work and organizational identification among teachers are closely associated with the quality of basic education. This study employed a longitudinal tracking design, conducting three follow-up surveys over a two-year period with 659 primary and secondary school teachers. It examined the bidirectional predictive relationship between thriving at work and organizational identification, while also testing whether psychological capital mediates this relationship longitudinally. Data analysis employing methods such as the cross-lagged model revealed that: (1) Both the simultaneous and sequential correlations between organizational identification, thriving at work, and psychological capital were significant. (2) Pre-test thriving at work significantly and positively predicted post-test organizational identification, whereas pre-test organizational identification did not significantly predict post-test thriving at work; (3) Mediation analysis indicated that psychological capital at Time 2 (T2) significantly mediated the longitudinal relationship between thriving at work at Time 1 (T1) and organizational identification at Time 3 (T3), indicating that T1 thriving at work could influence T3 organizational identification via T2 psychological capital. However, the reverse pathway was not supported. The findings of this study not only contribute to understanding the relationship between organizational identification and thriving at work, but also provide a scientific basis for educational administration departments to develop effective strategies aimed at enhancing teachers’ levels of thriving at work and strengthening their degree of organizational identification.</p>