According to attachment theory, mental representations are defined as dynamic cognitive guides that organize both perceptual and behavioral aspects of the self, attachment figure, and relationships with others. Based on this assumption, several studies had reported a relationship between attachment representations and the quality of care provided by mothers to their infants. This study explored on the relationship between maternal attachment representations, assessed by a narrative script task, and the quality of maternal care observed at home. Participants were 32 mothers between 19 and 44 years of age (M = 29.6, SD = 6.28) and their children between 8 and 10 months (M = 8.91, SD = 0.96). The results did not show a significant relationship between global scores of participants’ observed care (i.e., maternal sensitivity) and their attachment representations. However, a specific association was found between two dimensions of sensitivity (acceptance and active/animated interactions) and the narrative script that refers to a child’s physical injury event. Additionally, mothers who reported early separation experiences with their children showed a significant association between sensitivity and attachment representations on mother-child scripts. Moreover, these mothers showed lower scores on global sensitivity and on specific behavioral care dimensions, such as sensitive response and acceptance to child’s signals, than those of mothers that did not report separations early in their children’ lives.