By the year 2060, the number of adults over the age of 65 in the United States is projected to double to more than 90 million. In the absence of curative treatments for dementia and Alzheimer’s disease, identifying modifiable risk factors for cognitive decline has become a major public health priority. Vascular health is among the most widely studied modifiable risk factors. The presence of vascular conditions in midlife has been shown to increase risk for cognitive impairment and dementia in later life. Vascular health may also influence cognitive performance in non-demented older adults, particularly executive function (EF), potentially through age-related structural brain changes that are exacerbated by vascular burden. However, limited research has examined domain-specific cognitive consequences of midlife vascular risk or the mechanistic pathways linking vascular burden to later-life cognition. The present study used data from the National Alzheimer’s Coordinating Center to examine whether midlife vascular burden was associated with late-life EF and episodic memory (EM), whether these associations were mediated by WMH volume and GM composite volume, and whether education was linked to cognition through vascular burden and structural brain measures. Overall, findings provided partial support for the role of midlife vascular burden in late-life cognitive aging, although associations were not mediated by structural brain markers and the proposed education pathway was not supported. These findings highlight the importance of considering vascular health within a life-course framework and suggest that pathways linking vascular burden, brain structure, education, and cognition are complex.