Sustainable management of indoor and outdoor air quality is essential for protecting public health, enhancing well-being, and supporting resilient urban environments. Low-cost air quality sensors enable continuous, real-time monitoring of key pollutants and, when combined with data analytics, provide scalable and cost-effective insights for smart building operation and environmental decision-making. This pilot study evaluates an indoor–outdoor air quality monitoring system deployed at the Faculty of Electrical Engineering and Information Technologies in Skopje, with a focus on: (i) PM2.5 and PM10 concentrations and their relationship with meteorological conditions and human occupancy; (ii) sensor responsiveness and reliability in an educational setting; and (iii) implications for sustainable building operation. From January to March 2025, two indoor sensors (a classroom and a faculty hall) and two outdoor rooftop sensors continuously measured PM2.5 and PM10 at one-minute intervals. All sensors were calibrated against a reference instrument prior to deployment, while meteorological data were obtained from a nearby station. Time-series analysis, Pearson correlation, and multiple regression were applied. Indoor particulate levels varied strongly with occupancy and ventilation status, whereas outdoor concentrations showed weak to moderate correlations with meteorological variables, particularly atmospheric pressure. Moderate correlations between indoor and outdoor PM suggest partial pollutant infiltration. Overall, this pilot study demonstrates the feasibility of low-cost sensors for long-term monitoring in educational buildings and highlights the need for adaptive, context-aware ventilation strategies to reduce indoor exposure.