The specialization theory from Gary Becker is often used to explain the effect of women’s work on the risk of divorce. The main argument is that women with little work experience have higher economic costs to exit marriage. Using the Fertility and Family Surveys, we test for 16 countries to what extent women’s employment increases the risk of separation. We also more directly examine the role of economic exit costs in separation by investigating the effect of separated women’s work history during the union on women’s post-separation employment. The results imply that Becker was right to some extent, especially in contexts with little female employment support. However, in settings where women’s employment opportunities are more ample, sociological or psychological theories have probably more explanatory power to explain the causes and consequences of union dissolution.