Impaired vascular endothelial function has attracted attention as a prognostic indicator of cardiovascular prevention. The association between impaired endothelial function and cardiovascular risk in the asymptomatic population, however, has been poorly explored. We evaluated the association of brachial artery flow-mediated dilation (FMD) with Framingham-estimated 10-year cardiovascular disease (CVD) risk in subjects free of CVD, especially by cardiovascular risk profiles. In total, 680 adults aged 30-74 years were enrolled from Rongan and Rongshui of Liuzhou, Guangxi, China, through a cross-sectional study in 2015. In the full-adjusted model, the odds ratio for the estimated 10-year CVD risk comparing the low FMD (<6%) with the high FMD (≥10%) was 2.81 (95% confidence interval [CI]: 1.21, 6.53; P for trend = 0.03). In subgroup analyses, inverse associations between FMD and the estimated 10-year CVD risk were found in participants with specific characteristics. The adjusted odds ratios, comparing the 25th and the 75th percentiles of FMD, were 2.77 (95% CI: 1.54, 5.00) for aged ≥60 years, 1.77 (95% CI: 1.16, 2.70) for female, 1.59 (95% CI: 1.08, 2.35) for nonsmokers, 1.74 (95% CI: 1.02, 2.97) for hypertension, 1.59 (95% CI: 1.04, 2.44) for normal glycaemia, 2.03 (95% CI: 1.19, 3.48) for C-reactive protein ≥10 mg/L, and 1.85 (95% CI: 1.12, 3.06) for eGFR <106 mL/minute per 1.73 m2. Therefore, impaired endothelial function is associated with increased CVD risk in asymptomatic adults. This inverse association is more likely to exist in subjects with higher cardiovascular risk.