This study addresses the relationship between various family forms and the level of cognitive and non-cognitive skills among 15- to 16-year-old students. We measure cognitive skills using standardized scores in mathematics; non-cognitive abilities are captured by a composite measure of internal locus of control related to mathematics. A particular focus lies on father absence although we also examine the role played by co-residence with siblings and grandparents. We use cross-nationally comparable data on students participating in the Programme for International Student Assessment's release for 2012. By mapping inequalities by family forms across 33 developed countries, this study provides robust cross-country comparable evidence on the relationship of household structure with both cognitive and non-cognitive skills. The study produces three key results: first, the absence of fathers from the household as well as co-residence with grandparents is associated with adverse outcomes for children in virtually all developed countries. Second, this is generally true in terms of both cognitive and non-cognitive skills, although the disadvantage connected to both family forms is notably stronger in the former than in the latter domain. Finally, there is marked cross-national diversity in the effects associated with the presence in the household of siblings and especially grandparents which furthermore differs across the two outcomes considered.