A new body adiposity index (BAI) has been proposed that is expected to replace body mass index (BMI). We evaluated the correlations between metabolic syndrome risk factors and BAI, BMI, and other adiposity indices, such as waist circumference (WC), waist-to-hip ratio (WHR), and waist-to-height ratio (WHtR), by sex in the Korean population. We also evaluated whether BAI would be useful to diagnose metabolic syndrome. A total of 20,961 Korean adults who underwent health examinations were included in this study. The metabolic syndrome diagnostic criteria used in this study were those set by the American Heart Association/National Heart, Lung, and Blood Institute (AHA/NHLBI). In men (12,719), BMI and WHtR were more strongly correlated to metabolic syndrome risk than BAI, and in women (8,242), WHtR showed the strongest association with metabolic syndrome risk. BAI (area under the curve [AUC] = 0.678) presented lower discriminatory capacity than that of BMI (AUC = 0.836) for diagnosing metabolic syndrome. Moreover, BAI underestimated fat levels in men and women when considering the ability to discriminate overweight and obese individuals. In conclusion, WHtR and BMI in men, and WHtR in women may be better candidates than BAI to evaluate metabolic risk factors in Korean adults.