Road Safety Education (RSE) is widely known as a reliable determinant of the future results for what concerns health and welfare and as an undisputable factor which contributes to the social behavior of individuals and to their mid- and long-term road safety outcomes. However, its development has been relatively scarce in most countries, a fact which has contributed to letting matters as delicate as traffic crashes, largely explained by road misbehaviors, continue to be a prevalent problem, thus affecting the health of the community. The aim of this study was to describe the relationship between demographic and RSE-related variables and the self-reported road risky behavior of Spanish students. For this cross-sectional study, a representative sample of 4062 (51.5% males and 48.5% females) participants attending primary (47.5%), secondary (40.7%), and high school (11.7%) was gathered through a national survey on RSE and road behaviors. A set of significant associations between demographic factors, RSE variables, and self-reported road behaviors was found. Furthermore, Structural Equation Modelling (SEM) allowed us to establish that age and observed misbehaviors (positively), and attitudes towards road safety and risk perception (negatively), have a direct link with the road risky behavior of children and young people. The knowledge of traffic rules was not a significant predictor of road behavior. The results of this study show that, together with demographic factors such as age, RSE-related variables have an effect on the road behavior of children and young people. They also suggest the need for strengthening actions to be implemented in road safety (Road Safety Education) at scholar and community levels.