Most smokers who use electronic cigarettes (e-cigarettes) to stop smoking simultaneously use conventional cigarettes (dual users). We aimed to compare the prevalence of cardiovascular risk factors among dual users, cigarette-only smokers, and never smokers in Korean men. We used data acquired from Korean National Health and Nutrition Examination Survey (2013–2017) pertaining to 7,505 male participants aged 19 years or older. About 85% of e-cigarette users were dual users. Dual users had greater nicotine dependence and higher urinary cotinine levels than cigarette-only smokers. Dual users had more psychosocial and behavioural risk factors, including perceived high stress, depressive mood, high daily intake of energy, and obesity, than never smokers and cigarette-only smokers. The prevalence of metabolic syndrome (MetS) was higher among dual users, and their multivariate-adjusted prevalence odds ratio for MetS was 2.79 (P < 0.001) compared with never smokers and 1.57 (P = 0.038) compared with cigarette-only smokers. Given that most e-cigarette users are dual users and dual users are more vulnerable to cardiovascular risk factors than cigarette-only smokers and never smokers, more active treatment for smoking cessation and intensive lifestyle interventions for dual users should be considered with priority.