Background: Epidemiological studies on the association between levels of plasma vitamin E and first stroke risk are inconclusive. Methods: A nested, case–control study was conducted utilizing data on 115,337 hypertensive patients from the H-type Hypertension and Stroke Prevention and Control Project. The current analysis comprised 2193 cases of first stroke and 2193 controls matched for age, sex, and study site. Results: The mean plasma concentration of vitamin E was 12.37 (3.61) μg/mL. The smoothing curve showed a linear correlation between plasma vitamin E levels and the risk of the first stroke. Hypertensive patients with plasma vitamin E levels ≥14.1 μg/mL (Q4) had an increased risk of first stroke (adjusted odds ratios [OR]: 1.18; 95% confidence interval [CI]: 1.01, 1.37) compared with those with plasma vitamin E < 14.1 μg/mL (Q1–Q3). Sub-group analysis revealed that the relationship between plasma vitamin E (≥14.1.1 vs. P interaction = 0.035). Conclusions: This study suggests that higher levels of plasma vitamin E are associated with an elevated risk of first stroke among Chinese hypertensive patients.