Growing evidence has reported that a history of preeclampsia (PE) increases the risk of developing cardiovascular disease (CVD). Arterial stiffness plays a predictive role in CVD. Previous studies have demonstrated the close association between homocysteine (Hcy) level and arterial stiffness in community-based populations. This study was to assess whether Hcy level was independently associated with arterial stiffness in 168 women with a PE history who were analyzed at a 5-year follow-up. Brachial-ankle pulse wave velocity (baPWV) was measured by an automatic pulse-wave analyzer and a value >1,400 cm/s was defined as high arterial stiffness. Biochemical parameters were recorded and an Hcy value >10 μmol/L was defined as having hyperhomocysteine (H-Hcy). Variables that were significantly associated with baPWV were tested for independence by multivariate logistic regression analysis. We found that body mass index (OR 1.017, 95% CI 1.008–1.029), systolic blood pressure (OR 1.048, 95% CI 1.019–1.072), total cholesterol (OR 1.059, 95% CI 1.007–1.086), and Hcy level (OR 1.021, 95% CI 1.010–1.037) were independent determinants of baPWV in women with previous PE. Our findings indicate that Hcy pathway might be involved in arterial stiffness in women with a PE history. Whether Hcy would be a promising biomarker for serial stratified CVD risk management in these women deserves further evaluation on a large scale.