Objectives Mindfulness has been positively associated with affective well-being, which may be explained by improved affective disengagement from prior experiences. Methods We used a dynamic network approach to represent temporal interconnections between specific affective states (i.e., network density)-with less interconnected states indicating better affective disengagement-to investigate whether mindfulness predicted a lower network density. One-hundred twenty-five undergraduate students (M age = 22.87; SD = 5.06 years; 77.6% female) completed a 40-day ambulatory assessment, reporting on their affective experiences and state mindfulness six times a day, and either practiced mindfulness or were on a wait-list (control condition). Results We found that neither the mindfulness training, β = −.11, p = .222, nor state mindfulness, β = −.06, p = .484, were associated with affective network density. However, given prior research indicating the importance of prior meditation experience, we found that participants with prior meditation experience reported lower affective network density when they reported higher state mindfulness than participants without meditation experiences, β = −.20, p = .048. Conclusion The present study found that neither high levels of mindfulness nor a mindfulness training automatically improved affective disengagement in the form of lower network density. Rather, it seems that only those who were already familiar with practicing mindfulness and who were mindful in their daily life experienced easier disengagement from previous affective experiences. These findings may point toward a different, more complex, understanding of mindfulness in experienced meditators.