Efforts to improve child survival in lower-income countries typically focus on fundamental factors such as economic resources and infrastructure provision, even though research from post-industrial countries confirms that family instability has important health consequences. We tested the association between maternal union instability and children's mortality risk in Africa, Latin America and the Caribbean, and Asia using children's actual experience of mortality (discrete-time probit hazard models) as well as their experience of untreated morbidity (probit regression). Children of divorced/separated mothers experience compromised survival chances, but children of mothers who have never been in a union generally do not. Among children of partnered women, those whose mothers have experienced prior union transitions have a higher mortality risk. Targeting children of mothers who have experienced union instability-regardless of current union status-may augment ongoing efforts to reduce childhood mortality, especially in Africa and Latin America where union transitions are common.