This pilot study utilized phenomenological methodology to explore relational systems for ten mothers enrolled in family-centered substance use treatment. Participants described their experiences during motherhood and addiction. Analysis revealed themes that captured the interpersonal relationships of maternal substance use: (1) parent-child relationships in the context of maternal substance use disorders (SUDs), (2) interaction between romantic relationships and maternal substance use, and (3) intergenerational relationships among mothers and grandmothers. Mothers discussed these complicated and simultaneous roles and relationships that impacted their substance use and recovery within the context of family. Using ecostructural family therapy, we offer clinical recommendations with the aim of creating organizational change for families in recovery.