Growing evidence supports the role of mindfulness in regulating emotions in the general population. However, the interactive network of mindfulness facets and difficulties in regulating emotions is not well understood, which is specifically important for individuals involved in high-risk professions, such as first responders. The aim of this study was to investigate the interactive relations between mindfulness facets, acting with awareness, non-judging, describing, observing, and non-reacting, ability to regulate emotions and alcohol use in a sample of firefighters, including military veterans. A sample of 685 career firefighters, including 154 (22.5%) military veterans, who completed measures of mindfulness and difficulties in regulating emotions, was subjected to network analysis. Through network analysis, it was found that the mindfulness facet non-judging was negatively related to emotion regulation challenges, such as nonaccepting attitudes and lack of clarity, and positively related to deficits in goal-directed behavior. Acting with awareness was negatively related to goal-directed behavior deficits and impulsivity. Alcohol use was positively linked to impulsivity and negatively linked to the describing facet of mindfulness. Overall, emotion regulation difficulties were positively linked together, and positive links were found between most mindfulness facets. Directed network analysis identified non-judging and emotion regulation strategy as parental predictors. Non-judging appeared as a protective factor, supporting other mindfulness facets, while lack of emotion regulation strategies exacerbated emotion regulation challenges as a risk factor. This network analysis demonstrated the significance of acting with awareness and a non-judgmental attitude facet of mindfulness in fostering better emotion regulation and potentially playing a protective role against impulsivity and alcohol use in firefighters.