One of the sustainable development goals adopted by the United Nations is to ensure healthy lives and promote well-being for all. Tobacco consumption is a serious health problem that affects smokers and non-smokers exposed to secondhand smoke (SHS), particularly children. This study aims to describe parental perceptions of smoke-free rules, to analyze parental awareness about health risks associated with children’s exposure to SHS, and to describe the prevalence of avoidance behaviors related to tobacco smoke, according to parental smoking status. This study includes 1175 parents from a representative sample of 1511 Portuguese children aged 4 to 9 years old in 2016. Parents who were non-smokers reported a higher level of agreement regarding smoke-free rules at home, inside the car, at playgrounds, and near the school entrance than smokers. A higher percentage of nonsmoking parents agreed that children whose parents smoke at home are more likely to become smokers themselves. Nonsmoking parents reported adopting more avoidance behaviors regarding exposure to SHS. The findings indicate that parental exposure perceptions and avoidance behaviors towards SHS were lower and less frequent among smokers. Health education, smoking cessation programs and smoking bans are needed to raise parental awareness and to protect children from SHS exposure.