In response to the global impact of the COVID-19 pandemic, international and national authorities, including those in Catalonia (Spain), recognized the crucial need to ensure proper ventilation in classrooms, emphasizing the importance of safe and healthy indoor environments for face-to-face learning. The present work, conducted within the COVID-19 Sentinel Schools Network of Catalonia (CSSNC) framework, aimed to monitor carbon dioxide (CO2) and nitrogen dioxide (NO2) concentrations in 23 schools, ensuring a comprehensive sample regarding educational levels, daily scholar schedules, and classroom typologies distributed across the four provinces of Catalonia. The research spanned three study periods: March and April 2021, October 2021 to January 2022, and March to June 2022. Briefly, 28%, 25%, and 37% of classrooms surpassed the 700 parts per million (ppm) CO2 limit in each study period, respectively. Generally, CO2 averages were lower in preschool classrooms (mean ± SD = 486 ± 106 ppm), while high school classrooms displayed the highest CO2 concentrations (mean ± SD = 710 ± 253 ppm). Moreover, classrooms in towns (<30000 inhabitants) exhibited higher CO2 levels as compared to classrooms from schools located in cities. As for NO2, the highest averages were obtained in urban areas, particularly in the Barcelona metropolitan area (e.g. mean indoor levels of 24.56 μg m−3 as compared to 11.05 μg m−3 in towns). In addition, the Indoor/Outdoor ratio (I/O ratio) in towns was the lowest (0.60). These results, together with the higher concentration of CO2 indoors, could indicate poorer ventilation in town schools. The results of this study are anticipated to contribute to implementing evidence-based measures to improve indoor air quality (IAQ) in educational settings.