The chemical analysis of 553 school playground and classroom PM2.5 filters collected during the BREATHE sampling campaign in Barcelona, Spain, reveals a remarkable degree of spatial and temporal variability in ambient PM composition. Classroom air quality shows average PM2.5 concentrations of 37 μg m−3 (28% higher than outdoors), with much of this mass comprising carbon (including abundant cotton fibres), blackboard chalk particles and silicates. Where sandy playgrounds are present these exert a major influence on inhalable PM2.5 concentrations both indoors and outdoors. Throughout the city there is widespread contamination by metalliferous traffic particles, especially at schools located close to major urban highways where outdoor EC levels can be an order of magnitude higher than in peripheral, green belt schools. Penetration into the classroom of outdoor EC, ammonium sulphate and anthropogenic metals such as Cu, Sn, Sb, Zn and V is pervasive, especially during warmer months. In contrast, levels of nitrate and ammonium are much higher outdoors than in the classroom, especially during winter. During their work and play, schoolchildren across the city respire in a diversity of chemically differing atmospheric microenvironments.