Emotional availability (EA) reflects caregiving that is sensitive, non-intrusive, and non-hostile, and provides the child with structure to learn and safely explore their world. While variable, EA can be lower in mothers with problematic substance use compared to non-clinical samples. Despite strong support for a relation between impulsivity and problematic substance use (including as it relates to regulation of strong positive or negative emotion), its impact on EA has not been explored. This relationship was examined in a sample of 29 mothers who were attending substance use treatment. Video recordings of mother and child (under 4 years of age) playing were coded for EA and mothers completed a self-report questionnaire examining impulsivity. Given shared variance among types of impulsivity (cognitive, positive, and negative) and EA dimensions (sensitivity, structuring, non-intrusiveness, and non-hostility), canonical correlational analysis (CCA) was used to identify variables contributing most strongly to the relation between impulsivity and EA. A single function accounted for 56% of variance. Cognitive and negative emotional impulsivity contributed significantly to structuring and non-intrusiveness dimensions of EA. Positive emotional impulsivity made a smaller nonsignificant contribution but was noted to support EA sensitivity. Developing awareness of impulsivity and times that it may hinder or support EA may enhance the quality of parent-child relationship development, improve parenting confidence, and decrease risk for harsh or neglectful parenting.