While there is evidence that age-related changes in cognitive performance and brain structure can be offset by increased exercise, little is known about the impact on these of long-term high-effort endurance exercise. In a cross-sectional design with 12-month follow-up, we recruited older adults engaging in high-effort endurance exercise over at least twenty years, and compared their cognitive performance and brain structure with a non-sedentary control group similar in age, sex, education, IQ, and lifestyle factors. Our findings showed no differences on measures of speed of processing, executive function, incidental memory, episodic memory, working memory, or visual search for older adults participating in long-term high-effort endurance exercise, when compared without confounds to non-sedentary peers. On tasks that engaged significant attentional control, subtle differences emerged. On indices of brain structure, long-term exercisers displayed higher white matter axial diffusivity than their age-matched peers, but this did not correlate with indices of cognitive performance.