Purpose: Cardiovascular disease remains the global leading cause of death. We evaluated at baseline the association between the adherence to eight a priori high-quality dietary scores and the prevalence of individual and clustered cardiovascular risk factors (CVRF) in the PREDIMED-Plus cohort. Methods: All PREDIMED-Plus participants (6874 men and women aged 55–75 years, with overweight/obesity and metabolic syndrome) were assessed. The prevalence of 4 CVRF (hypertension, obesity, diabetes, and dyslipidaemia), using standard diagnoses criteria, were considered as outcomes. The adherence to eight a priori-defined dietary indexes was calculated. Multivariable models were fitted to estimate differences in mean values of factors and prevalence ratios for individual and clustered CVRF. Results: Highest conformity to any dietary pattern did not show inverse associations with hypertension. The modified Mediterranean Diet Score (PR = 0.95; 95% CI 0.90–0.99), Mediterranean Diet Adherence Score (MEDAS) (PR = 0.94; 95% CI 0.89–0.98), the pro-vegetarian dietary pattern (PR = 0.95; 95% CI 0.90–0.99) and the Alternate Healthy Eating Index 2010 (PR = 0.92; 95% CI 0.87–0.96) were inversely associated with prevalence of obesity. We identified significant inverse trend among participants who better adhered to the MEDAS and the Prime Diet Quality Score (PDQS) in the mean number of CVRF across categories of adherence. Better adherence to several high-quality dietary indexes was associated with better blood lipid profiles and anthropometric measures. Conclusions: Highest adherence to dietary quality indexes, especially Mediterranean-style and PDQS scores, showed marginal associations with lower prevalence of individual and clustered CVRF among elderly adults with metabolic syndrome at high risk of cardiovascular disease.