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Although it is known that mothers with substance-use disorders struggle to provide adequate parenting to their children, little is understood about the mechanisms behind this. This cross-sectional study uses an attachment perspective to examine whether reflective functioning mediates the relationship between mental representations of caregiving and maternal sensitivity, in an ethnically diverse sample of 142 substance-dependent mothers (M = 29.81, SD = 5.85 years of age) and their toddlers (M = 24.04, SD = 15.15 months of age). Data were baseline measures from 2 randomized controlled trials. The 3 variables of primary interest were positively correlated. As expected, there was a significant relationship between mental representations of caregiving and maternal sensitivity that was largely explained by reflective functioning. Confounding and alternate explanations were not supported by secondary data analyses. The findings underscore the importance of reflective functioning in positive parenting within this high-risk population of mothers, and they provide support for the development of attachment-based interventions.