ABSTRACT This study examines the dynamic interplay between workplace stressors, appraisals, and their affective outcomes through a daily diary design. Grounded in the Challenge‐Hindrance Stressor Framework (CHSF) and Transactional Theory of Stress, four stressors—role conflict, role overload, emotional demands, and workload—were evaluated for dual appraisals as challenges and hindrances. Our investigation expands these models by assessing how the same stressors can simultaneously elicit both challenge and hindrance appraisals at both within‐ and between‐person levels. Results reveal that all stressors were appraised as both challenges and hindrances, challenging CHSF's binary classification. Furthermore, both appraisal types mediated relationships with affective outcomes, with significant mediation observed for negative affect but not positive affect. Challenge appraisals were unexpectedly linked to increased negative affect, highlighting the complex consequences of stressors. The findings underscore the need for more nuanced and dynamic models that integrate stressor appraisals and their proximal affective outcomes, advancing theoretical frameworks in occupational stress research.