Research has demonstrated that preschool teachers are particularly prone to develop burnout symptoms, such as emotional exhaustion. However, which workplace conditions are particularly related to burnout symptoms in preschool teachers remains widely unknown. Hence, this study aims to disentangle personal characteristics (e.g. educational degree, working experience) and structural as well as social conditions of preschool teachers’ work environment (e.g. teacher–child ratio, team climate) in relation to emotional exhaustion. We draw on data collected from a nation-wide sample of 1,394 preschool teachers nested in 204 preschools. Multilevel analysis demonstrated that center differences explained only 5.8% of the overall variance in levels of emotional exhaustion. Emotional exhaustion was strongly associated with social experiences at the workplace, but much less with structural or personal job conditions. Hence, practical interventions should also focus on social aspects, such as team cohesion and dealing with challenges in parent-teacher collaborations.