To understand the population impact of e-cigarettes, it is important to examine the profile of e-cigarette users. The purpose was to examine the characteristics, patterns of e-cigarette use and smoking status of a random sample of vapeshops customers in Greece. Fourteen vapeshops were randomly selected in the region of Athens. Every third customer buying products for personal use was recruited by a researcher visiting the vapeshops. Current smoking status was assessed by measuring exhaled carbon monoxide (eCO), with a value ≥ 7 ppm being used to classify subjects as current smokers. A questionnaire was used to examine past smoking status, patterns of e-cigarette use, changes in health status and experienced side effects. Logistic regression analysis was performed to identify correlates of being a former smoker. A total of 309 participants were analyzed, with 82.5% being daily e-cigarette users. The vast majority (98%) were smokers before e-cigarette use initiation, with 69.6% of them having eCO < 7 ppm (former smokers). Only 1% were never smokers, and 1% had quit smoking before e-cigarette use initiation; all of them had eCO < 7 ppm. Most participants were using third-generation devices (61.8%) and were using non-tobacco flavors (58.9%). The average liquid consumption was 5 mL/day. Most participants experienced health benefits, mainly improvement in physical status, exercise capacity, olfactory and gustatory senses, while the most common side effects were throat irritation and cough. The strongest correlate of being a former smoker was daily e-cigarette use. Vapeshops customers in Greece are mainly current and former smokers with the majority of them having quit smoking. E-cigarette use by never smokers is rare and none of them subsequently initiate smoking.