The use of electronic cigarettes (e-cigarettes) persists in Brazil, despite restrictions on sales, imports, and advertising. This study aimed to identify the prevalence of e-cigarette use and user profiles among university students. This cross-sectional study used a convenience sample of 3083 university students (female = 2253, male = 830;
M
=26.1;
SD
=8.43) who completed an online survey. We employed logistic regression models and network analysis to determine the profile of e-cigarette users. The prevalence of e-cigarette use in the past year was 12.2% (
n
=377). Men, single individuals, Caucasians, secular individuals, and non-heterosexual individuals were more likely to engage in e-cigarette use. Intense use of alcohol, tobacco products, and illicit drugs increased the likelihood of e-cigarette use. Brazilian college students continue to use electronic cigarettes despite the prohibition. The pattern of alcohol abuse and tobacco product use among e-cigarette users is concerning. These risky behaviors render young and highly educated individuals targets for public policies to control and regulate electronic cigarettes in the country.