Introduction Although daily walking implies several potential benefits for the health and well-being of people, and, besides the raise of more “walkable” cities, it is currently being promoted as an active transportation means that is rich in benefits for its users, road risks affecting pedestrians, together with their high vulnerability to suffer severe injuries as a consequence of traffic crashes, have turned into a relevant concern for both policymakers and public health practitioners. In this regard, risky and positive (proactively safe) behaviors have acquired a substantial relevance for the study and prevention of traffic causalities involving different road users, including pedestrians. Objective The objective of this study was to thoroughly describe the validation of an instrument for measuring the walking risky and positive behavior on the road, using the Walking Behavior Questionnaire (WBQ). Methods This cross-sectional study analyzed the data from 1070 Spanish pedestrians answering a questionnaire on road behaviors. The data were analyzed using the competitive Confirmatory Factor Analysis (CFA), thus obtaining basic psychometric properties, testing convergent validity and predictive value, and presenting an optimized structure for the scale. Results The obtained findings suggest that the WBQ has a clear dimensional structure, items with high factorial weight, good internal consistency and reliability and an adequate convergent validity with variables theoretically associated with road behaviors. Conclusion The results of this study endorse the psychometric value of the WBQ for measuring errors, violations and positive behaviors of pedestrians. This questionnaire might have relevant applications in the practical field, since, apart from having good psychometric properties, it introduces items related to social and technological trends (e.g., the use of cellphones) that may compromise pedestrians’ safety. This can be particularly useful for designing behavioral-based interventions and educational programs, focused on road risk reduction and on the promotion of safe walking behavior.