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Antihypertensives have been linked to new-onset diabetes (NOD) and different classes of antihypertensives may alter the risk for the development of NOD; however, the effect of different antihypertensives on the development of NOD in women with hypertension and coronary artery disease (CAD) has not been well studied. The purpose of this study is to investigate the association between usage of different antihypertensive drugs and the development of NOD in female patients with hypertension and CAD. Data in this retrospective cohort study were obtained from claim forms submitted to the Taiwan Bureau of National Health Insurance in central Taiwan during the period 2006–2011. We estimated the odds ratios (OR) to approximate the relative risk of NOD development associated with antihypertensive drug use. Of the 20,108 female patients with CAD at baseline, 2288 patients developed NOD during the 6-year follow-up. Subjects treated with angiotensin-converting enzyme (ACE) inhibitors (OR, 0.92; 95% confidence interval [CI], 0.84–1.00), angiotensin receptor blockers (OR, 0.92; 95% CI, 0.82–0.99), and alpha-blockers (OR, 0.88; 95% CI, 0.79–0.98) in the adjusted analyses had greater reductions of the risk than among nonusers. Patients who took diuretics (OR, 1.10; 95% CI, 1.01–1.20), beta-blockers (OR, 1.12; 95% CI, 1.04–1.21), and calcium channel blockers (OR, 1.10; 95% CI, 1.02–1.18) were at high risk of developing NOD than nonusers. Vasodilators were not associated with risk of NOD. We conclude that women with hypertension who take ACE inhibitors, angiotensin receptor blockers, and alpha-blockers are at lower risk of NOD and that use of diuretics, beta-blockers, and calcium channel blockers was associated with a significantly increased risk of developing NOD during the 6-year follow-up.