Brain activity continuously and spontaneously fluctuates during tasks of sustained attention. This spontaneous activity reflects the intrinsic dynamics of neurocognitive networks, which have been suggested to differentiate moments of externally directed task focus from episodes of mind wandering. However, the contribution of specific electrophysiological brain states and their millisecond dynamics to the experience of mind wandering is still unclear. In this study, we investigated the association between electroencephalogram microstate temporal dynamics and self-reported mind wandering. Thirty-six participants completed a sustained attention to response task in which they were asked to respond to frequently occurring upright faces (nontargets) and withhold responses to rare inverted faces (targets). Intermittently, experience sampling probes assessed whether participants were focused on the task or whether they were mind wandering (i.e., off-task). Broadband electroencephalography was recorded and segmented into a time series of brain electric microstates based on data-driven clustering of topographic voltage patterns. The strength, prevalence, and rate of occurrence of specific microstates differentiated on- versus off-task moments in the prestimulus epochs of trials preceding probes. Similar associations were also evident between microstates and variability in response times. Together, these findings demonstrate that distinct microstates and their millisecond dynamics are sensitive to the experience of mind wandering.