Waste management is a severe environmental and social concern in Latin America. However, it is not just a Latin American problem, for example, of the 17 Sustainable Development Goals of the UN 2030 Agenda for Sustainable Development; at least 12 have a direct link with solid waste management. In this context, understanding what factors affect the behavior of residential waste separation helps to build effective environmental campaigns. The selective collection effectively of urban solid waste in a city is fundamentally related to the positive behavior of individuals from that society. Consequently, this study aimed to propose steps to maximize engagement concerning participation in the system of selective collection by the population of the Federal District of Brazil. In order to achieve this goal, as a first step, it is necessary to know the variables that lead to this type of behavior, since several different factors determine human behavior. In the literature, the theory of planned behavior (TPB) has been widely used to analyze this phenomenon. The TPB postulates that individual behavior is determined behavioral intentions, where these behavioral intentions are a function of three determinants; an individual's attitude toward behavior, subjective norms and perceived behavioral control. Attitude toward a behavior is about the individual’s positive or negative feelings about performing the behavior. Subjective norm is defined as the individual’s perception that people relevant to the individual should perform the behavior in question. Perceived behavior control refers to the individual’s perception of the difficulty or ease of performing a behavior. In this study, a quantitative exploratory analysis is performed using structural equation modeling. A questionnaire was applied to 120 individuals from the Federal District; the survey was taken in order to achieve a better representation of the citizen of the district. Based on this data, a TPB model was validated using the Partial Least Squares (PLS) technique. In particular, the SmartPLS software was used. The result of this analysis points out the validate and reliability of the measurement model. Additionally, the analysis of the structural model determines it is possible to explain the behavior by 47.2%. In short, the variable with the most significant contribution to the prediction of waste separation behavior is the perceived behavioral control; This variable is responsible for 27.8% of the variance explained by the endogenous variable. This result is different from other studies where the three exogenous variables of the TPB model explain the intention. We believe that this may be due to citizens homogeneously aware of the problem of residential waste management. Last but not less, the study proposes a behavior mobilization strategy, integrating the pillars of awareness, strategic facilitation, and transparency into an action plan that is the basis for the development of pro-environmental behavior.