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Background E-cigarettes may be effective smoking cessation aids and their use by smokers has been growing rapidly. It is important to observe and assess natural patterns in the use of e-cigarettes whilst experimental data accumulates. This paper reports the prevalence of e-cigarette awareness, beliefs and usage, including brand choice, and characterises the socio-demographic and smoking profile associated with current use, among the general population of smokers and recent ex-smokers. Methods Data were obtained from 3538 current and 579 recent ex-smokers in a cross-sectional online survey of a national sample of smokers in Great Britain in November and December 2012. Differences between current and recent ex-smokers in the prevalence of e-cigarette awareness, beliefs and usage were examined and the socio-demographic and smoking profile associated with current use of e-cigarettes was assessed in a series of simple and multiple logistic regressions. Results Ninety-three percent of current and recent ex-smokers (n = 3841) were aware of e-cigarettes. Approximately a fifth (n = 884) were currently using e-cigarettes, whilst just over a third (n = 1507) had ever used them. Sixty-seven percent of the sample (n = 2758) believed e-cigarettes to be less harmful than cigarettes; however, almost a quarter (n = 994) remained unsure. Among both current and recent ex-smokers, the most popular reasons for using were health, cutting down and quitting (each > 80%) and 38% used the brand ‘E-lites’. Among current smokers who were aware of but had never used e-cigarettes, approximately half (n = 1040) were interested in using them in the future. Among current smokers, their use was associated with higher socio-economic status (OR = 1.48, 95%CI = 1.25–1.75), smoking more cigarettes (OR = 1.02, 95%CI = 1.01–1.03) and having a past-year quit attempt (OR = 2.82, 95%CI = 2.38–3.34). Conclusions There is a near universal awareness of e-cigarettes and their use appears to be common among smokers in Great Britain although a quarter of all smokers are unsure as to whether e-cigarettes are less harmful than cigarettes. E-lites – a brand that delivers a low dose of nicotine – is the most popular. E-cigarette users appear to have higher socio-economic status, to smoke more cigarettes per day and to have attempted to quit in the past year., Highlights • There is now near universal awareness of e-cigarettes. • Use is common among smokers. • Quarter of all smokers unsure as to whether they are less harmful than cigarettes. • E-lites – a brand that delivers a low dose of nicotine – is the most popular. • Users have higher SES, smoke more heavily and have attempted to quit recently.