Social relationships shape adult health in profound ways. This study informs our understanding of this association by investigating how the transitions, timing, and exposures to marriage are associated with types of biological risk presumed to serve as pathways to disease and disability. Drawing on the 2005–2006 National Social Health and Aging Project (N = 1,062), the authors evaluated how marital biography was associated with cardiovascular, metabolic, and chronic inflammation risk. The results showed that the effects of marital biography were highly sensitive to gender, the dimension of marital biography, and type of biological risk. For example, marital exposure was protective of cardiovascular risk for women, but not men, whereas an earlier age at first marriage had a pernicious effect on chronic inflammation among men, but not women. Health behaviors did not explain these associations. The implications of these findings are discussed as they pertain to under-the-skin risk processes and chronic morbidity.