Stressor‐evoked cardiovascular reactivity, trait positive emotionality, and negative emotionality are all associated with cardiovascular disease. It is unknown, however, whether cardiovascular reactivity may constitute a pathway by which trait positive or negative emotionality relates to disease risk. Accordingly, this study modeled the cross‐sectional relationships between trait positive and negative emotionality, stressor‐evoked cardiovascular reactivity, and severity of a subclinical vascular marker of cardiovascular risk, carotid artery intima‐media thickness (CA‐IMT). The sample consisted of healthy, midlife adults free from clinical cardiovascular disease (N = 286; ages 30–54; 50% female). Trait positive and negative emotionality were measured by three questionnaires. Heart rate and blood pressure reactivity were assessed across three stressor tasks. CA‐IMT was assessed by ultrasonography. Latent factors of positive and negative emotionality, blood pressure reactivity, heart rate reactivity, and CA‐IMT were created using structural equation modeling. Greater negative emotionality was marginally associated with more CA‐IMT (β = .21; p = .049), but lower blood pressure reactivity (β = −.19; p = .03). However, heightened blood pressure (β = .21; p = .03), but not heart rate reactivity (β = −.05; p = .75), associated with greater CA‐IMT. Positive emotionality was uncorrelated with cardiovascular reactivity (blood pressure: β = −.04; p = .61; heart rate: β = .16; p = .11) and CA‐IMT (β = .16; p = .07). Although trait negative emotionality associates with a known marker of cardiovascular disease risk, independent of positive emotionality, it is unlikely to occur via a stressor‐evoked cardiovascular reactivity pathway.