Background: This study examines primary schoolchildren’s perceptions of e-cigarettes and tobacco cigarettes, and associations with parental smoking, vaping and socioeconomic status. Methods: Survey of 2218 10–11-year-old children in 73 schools in Wales. Results: Overall, 36% reported that a parent figure smoked compared to 21% for vaping, with parental smoking lower in affluent families (OR = 0.72; 95% CI = 0.68 to 0.76). Overall, 1% had tried a cigarette, while 5% had tried an e-cigarette. Most said they would not smoke or vape in 2 years’ time; susceptibility to vaping (20%) was higher than smoking (12%). Exposure to and perceptions of tobacco cigarettes were more positive for children of smokers. Having a parent who vaped was associated with exposure to and positive perceptions of e-cigarettes, but not smoking. Most children perceived e-cigarettes as used by adults to stop smoking (64%). Susceptibility to smoking (OR = 0.57; 95% CI = 0.41 to 0.79) and vaping (OR = 0.78; 95% CI = 0.62 to 0.99) were lower among children who perceived e-cigarettes as cessation aids. Conclusions: Parental smoking continues to be concentrated in poorer families. This study provides no evidence that parental vaping in the absence of smoking is associated with more positive perceptions of tobacco cigarettes. Communicating to children the role of e-cigarettes as cessation devices for smokers may help to limit their appeal to young people.