Investigations of the educational implications of children's exposure to air pollutants at school are crucial to enhance our understanding of the hazards for children. Most of the existing literature is based on studies performed in North America and Europe. Further investigation is required in low-and middle-income countries, where there are important challenges related to public health, transportation, environment, and education sector. In response, in this present study, we studied the association between proximity of schools to roads and the academic achievement of the students in the Federal District, Brazil. We accessed academic achievement data at the student level. The data consist of 256 schools (all the public schools in the FD) and a total of 344,175 students (all the students enrolled in the public schools in the FD in 2017-2020). We analyzed the association between the length of all roads within buffers around schools and student-level academic performance using mixed-effects regression models. After adjustments for several covariates, the results of the primary analysis indicate that the presence of roads surrounding schools is negatively associated with student-level academic performance in the FD. This association varies significantly depending on the buffer size surrounding schools. We found that the highest effects occur in the first buffer, with 250 m. While in the first buffer we estimated that an increase of 1 km of length of roads around schools was associated with a statistically significant decrease of 0.011 (95%CI: 0.008; 0.013) points in students' grades (students' academic performance varies from 0 to 10), in the buffer of 1 km we found a decrease of 0.002 (95%CI: 0.002; 0.002) points in the student-level academic performance. Findings from our investigation provide support for the creation of effective health, educational and urban planning policies for local intervention in the FD. This is essential to improve the environmental quality surrounding schools to protect children from exposure to environmental hazards.