While regular physical exercise as a recovery activity has an important role regarding employees’ well-being, employees seem to engage less in physical exercise after stressful workdays—pointing to a paradoxical pattern. Extending the recovery paradox (Sonnentag, 2018) applied to physical exercise and drawing from perspectives on energetic and self-regulatory resource loss and recovery, we integrate psychological detachment right after work as an explaining psychological mechanism in the paradoxical pattern between job stressors, physical exercise, and energetic well-being. We collected daily diary data from 93 employees on 514 days over two consecutive workweeks. Results of our two-level path model suggest that psychological detachment right after work explains the paradoxical pattern between job stressors (workload and self-control demands) and time spent on physical exercise. However, we did not find a serial indirect effect from job stressors to next-morning energetic well-being (vigor and fatigue) via psychological detachment and time spent on physical exercise. Our study suggests a new perspective on the role of psychological detachment, namely as a prerequisite instead of an outcome of physical exercise after stressful workdays. This new perspective has implications for future research and practical interventions. (PsycInfo Database Record (c) 2024 APA, all rights reserved) (Source: journal abstract)