Background: E-cigarettes (ECs) seem to be a less harmful alternative for conventional cigarettes, however, very little is still known about the exposure to some elements, which are the components of this device and may contaminate the nicotine liquid. The aim of this study is to assess whether e-cigarette users are more exposed to 12 elements detected in aerosol than non-smokers and conventional cigarette smokers, using their concentrations in urine as exposure biomarkers. Methods: A cross-sectional, group-based survey was carried out using 90 volunteers classified into groups of non-smokers, EC-only users, dual EC users-cigarette smokers and cigarette-only smokers. Using inductively coupled plasma mass spectrometry (ICP-MS) and electrothermal atomic absorption spectrometry (ETAAS), Cr, Ni, Co, Ag, In, Mn, Ba, Sr, V, Sb, Cd and Pb levels were measured in spot urine samples. Among the selected groups, a comparison was made using the analysis of covariance and correlations with EC usage pattern were assessed by multiple linear regression. Results: Element concentrations in urine of EC-users were not significantly different from the levels found in non-smokers and smokers. Only in the case of Ba, Ni and Sb was a significant correlation found in relation to some e-cigarette usage patterns. Conclusion: Transfer of the investigated elements to the EC aerosol was not found to be a substantial source of exposure in EC users who quitted smoking.