Mothers with a substance use disorder (SUD) are at risk for maladaptive parenting practices, and have heightened likelihood of having experienced childhood adversity themselves. In addition, parental reflective functioning (PRF), a capacity underlying sensitive caregiving, is often low in mothers with SUD. This study examines the relationship between PRF and aversive (emotional, physical, sexual abuse and neglect) and adaptive (safety and competence) experiences, in different developmental phases (early childhood, latency, and adolescence) in mothers with a SUD. A sample of 43 mothers with small children were interviewed with the Parental Developmental Interview to assess PRF, and they completed the Traumatic Antecedents Questionnaire regarding aversive and adaptive experiences. In addition, we used the Hopkins Symptoms Checklist-10 to control for mental health status and a battery of neuropsychological tests to control for executive functions. Results indicated that adaptive experiences in early childhood were positively related to PRF, and that experience of emotional abuse was negatively related to PRF. When separating the group of mothers in two sub-groups based on PRF level, results showed that mothers with negative to low PRF had significantly more experiences of adversities in early childhood and latency, and significantly less adaptive experiences in early childhood, latency and adolescence, compared to mothers with moderate to high PRF. In addition, mothers with adequate to high PRF reported experiencing significantly more types of adaptive experiences, and significantly less adversities compared to mothers with negative to low PRF. Results are discussed in relation to developmental trauma, resilience, epistemic trust and mistrust.