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Background Low maternal self-efficacy and high levels of anxiety, depression, and stress can be triggered in adolescent mothers due to an incomplete development process that makes them physically or psychologically unprepared for the responsibilities of motherhood and parenting. These factors may be linked to difficulties with their children’s social-emotional development. The present study aims to: (a) analyze the relationship between maternal self-efficacy and stress, depression, and anxiety levels in low-income adolescent mothers; (b) examine the relationship between maternal self-efficacy and well-being with children’s social-emotional development; and (c) describe the effects of maternal self-efficacy on children’s social-emotional development, mediated by maternal well-being. Methods A sample of 79 dyads comprising low-income Chilean adolescent mothers aged from 15 to 21 years old (M = 19.1, SD = 1.66) and their children aged 10 to 24 months (M = 15.5, SD = 4.2) participated in this research. A set of psychometric scales was used to measure maternal self-efficacy (Parental Evaluation Scale, EEP), the mothers’ anxiety and depression (Hospital Anxiety and Depression Scale, HADS), maternal stress (Parental Stress Scale, PSS), and the children’s social-emotional development (Ages and Stages Questionnaire Socio-emotional, ASQ-SE). Bivariate analyses and mediation models were employed to estimate and test the relevant relationships. Results A bivariate analysis showed that maternal self-efficacy was negatively related to the mother’s anxiety, depression, and stress. Moreover, there was a significant relationship between maternal self-efficacy and maternal stress, and children’s self-regulation and social-emotional development. Maternal self-efficacy, mediated by maternal anxiety, depression, and stress scores, had a significant effect on the development of children’s self-regulation. Conclusions The results confirm the importance of adolescent mothers’ emotional well-being and maternal self- efficacy with respect to their children’s social-emotional development. This makes it necessary to have detailed information about how emotional and self-perception status influences a mother’s role in the development of her children.