As women age, especially after menopause, cardiovascular disease (CVD) prevalence rises, posing a significant global health concern. Regular exercise can mitigate CVD risks by improving blood pressure and lipid levels in postmenopausal women. Yet, the optimal exercise modality for enhancing vascular structure and function in this demographic remains uncertain. This study aims to compare five exercise forms to discern the most effective interventions for reducing cardiovascular risk in postmenopausal women. The study searched PubMed, Web of Science, Cochrane, EBSCO, and Embase databases. It conducted a network meta-analysis (NMA) of randomized controlled trials (RCTs) on five exercise interventions: continuous endurance training (CET), interval training (INT), resistance training (RT), aerobic combined with resistance training (CT), and hybrid-type training (HYB). Outcome measures included carotid artery intima-media thickness (IMT), nitric oxide (NO), augmentation index (AIx), pulse wave velocity (PWV), and flow-mediated dilatation (FMD) of the brachial artery. Eligible studies were assessed for bias using the Cochrane tool. A frequentist random-effects NMA was employed to rank exercise effects, calculating standardized mean differences (SMDs) with 95% confidence intervals (CIs). The analysis of 32 studies (n = 1,427) indicates significant increases in FMD with CET, INT, RT, and HYB in postmenopausal women. Reductions in PWV were significant with CET, INT, RT, CT, and HYB. AIx decreased significantly with INT and HYB. CET, INT, and CT significantly increased NO levels. However, no significant reduction in IMT was observed. SUCRA probabilities show INT as most effective for increasing FMD, CT for reducing PWV, INT for decreasing AIx, CT for lowering IMT, and INT for increasing NO in postmenopausal women. The study demonstrates that CET, INT, RT, and HYB have a significant positive impact on FMD in postmenopausal women. Furthermore, all five forms of exercise significantly enhance PWV in this population. INT and HYB were found to have a significant positive effect on AIx in postmenopausal women, while CET, INT, and CT were found to significantly improve NO levels. For improving vascular function in postmenopausal women, it is recommended to prioritize INT and CT exercise modalities. On the other hand, as CET and RT were not ranked at the top of the Sucra value ranking in this study and were less effective than INT and CT as exercise interventions to improve vascular function in postmenopausal women, it is not recommended that CET and RT be considered the preferred exercise modality.