<p>Mind-wandering (MW), a form of attentional disengagement during operational tasks, has emerged as a critical cognitive risk factor for unsafe behavior in high-risk industries. Moreover, the disruption of circadian rhythms induced by shift work further amplifies the risks associated with MW in operational contexts. However, existing research has largely relied on short duration experiments conducted under controlled laboratory conditions, leaving the neural mechanisms of MW in authentic high risk operational contexts insufficiently understood. Even fewer studies have empirically examined how shift work influences MW from the perspective of brain network organization. In response to this research gap, the present study employs Lab-in-the-Field experiments to analyze the brain network characteristics of workers in high-risk industries, aiming to elucidate the potential mechanisms by which MW and shift work jointly impact operational safety. The results demonstrated that MW significantly prolonged response times, and that shift work further exacerbated this negative effect. EEG based brain network analysis further showed that MW was accompanied by changes in brain network resource allocation, with a particularly evident decline in hub efficiency in the left prefrontal cortex. Moreover, shift work was found to affect cognitive states predominantly by altering the structural topology of brain networks, rather than by simply modulating the overall strength of functional connectivity. This study validates the brain network reorganization underlying MW and provides scientific evidence for developing cognitive state monitoring tools and targeted intervention strategies based on brain network topological features.</p>