Individuals exposed to both job loss and marital dissolution are likely to be highly disadvantaged, having experienced stresses and losses in the two primary domains of life. Moreover, recent literature finds that exposure to one event tends to increase the risk of the other. However, next to nothing is known about the size or composition – or changes therein – of the divorced/separated and unemployed (DSU) subpopulation. Using large, nationally representative, repeated cross-sectional datasets extending back to 1984, we aim to fill this gap for the UK. We give a descriptive account of the prevalence and social distribution of DSU, and of the cross-sectional association between its two component states: among which groups, by education and gender, does being either divorced/separated or unemployed most strongly imply a heightened risk of also being the other, and how has this changed over time? We find stable and strong educational inequality in DSU, while the gender gap has narrowed and recently closed. The association between the two states is stronger among men; has weakened strikingly over the time period we consider, for both men and, especially, women; and is educationally stratified among men but not women. Contrary to expectations, higher-educated men in one of the two states are most likely to also be in the other. Possible explanations and further questions are discussed. In particular, we highlight the possibility that over this time period the divorced/separated have become more like the general population, rather than a negatively selected subgroup among whom unemployment is a particular risk.