Background: Education in road safety (also known as Road Safety Education—RSE) constitutes, nowadays, an emergent approach for improving present and future road behaviors, aiming at taking action against the current, and concerning, state-of-affairs of traffic crashes, through a behavioral perspective. In the case of children, and despite their overrepresentation in traffic injury figures, RSE-based strategies for behavioral health in transportation remain a “new” approach, whose impact still needs to be empirically tested. Objective: The aim of this study is to assess the impact of three key road safety skills of the Positive Attitudes, Risk perception and Knowledge of norms (PARK) model, addressed in RSE-based interventions, on the safe road behavior of Spanish children. Methods: For this cross-sectional study, a representative sample of 1930 (50.4% males and 49.6% females) Spanish children attending primary school, with a mean age of 10.1 (SD = 1.6) years, was gathered from 70 educational centers across all Spanish regions, through a national study on RSE and road safety. Results: Road safety skills show a positive relationship with children’s self-reported safe behaviors on the road. However, the knowledge of traffic norms alone does not predict safe behaviors: it needs to be combined with risk perception and positive attitudes towards road safety. Furthermore, the degree of exposure to previous RSE interventions was shown to have an effect on the score obtained by children in each road safety skill; on the other hand, road misbehaviors observed in parents and peers had a negative impact on them. Conclusion: The outcomes of this study suggest that education in road safety is still a key process for the acquisition of safe habits, patterns and behaviors among young road users