This work examines whether the increase of single parenthood in Italy and Spain, specifically amongst women in an unfavourable socioeconomic position, has repercussions for child well-being, understood here as material deprivation. In particular, our main objective is to analyse the possible differential impact of single parenthood on children’s material deprivation in relation to mothers’ level of education. Using the 2014 EU-SILC Module on material deprivation, we identify five areas of child deprivation based on the EU-MODA approach: nutrition, clothing, education, leisure, and social life. In the case of Italy, our main results indicate that, compared to children from two-parent households, children of single mothers with a low level of education have a higher risk of nutrition and clothing deprivation. In Spain, living in a single-parent household is associated with a higher risk of deprivation in terms of social life for those children whose mothers do not have a high level of education. Therefore, the findings suggest that in both countries the growth of single parenthood amongst women with a lower educational level may have an impact on child well-being inequality. This article contributes empirical data to the growing literature on the rise of child poverty in Southern European countries.