Technological acceleration is intensifying job demands (IJDs), referring to work intensification, intensified job- and career-related planning and decision-making demands, and intensified learning demands at work. IJDs mean new challenges for workers but recovery from work during off-job time through psychological detachment from work may help employees to maintain their well-being in the context of IJDs. The present study examined the associations between IJDs and emotional exhaustion and the buffering role of psychological detachment in these relationships. Cross-sectional data were collected from four Finnish trade unions in 2018 (N = 3,181). Data were analyzed by structural equation modeling (SEM). Higher IJDs were related to greater emotional exhaustion, and greater psychological detachment from work to lower emotional exhaustion. Of IJDs, work intensification had the strongest relationship with higher emotional exhaustion. As expected, psychological detachment attenuated the positive relationship between IJDs and emotional exhaustion. In general, the group-specific findings for blue-collar and white-collar workers were in line with the results found for the data as a whole. The results underline the beneficial role of psychological detachment from work as a strategy for replenishing resources that protects employees’ occupational well-being in the presence of high IJDs. The potential risks of IJDs in today’s workplaces should be recognized and employees’ opportunities to mentally detach from work during free time should be supported.