In this paper, we provide a detailed description of the application of passive sampling with Carbopack X tubes followed by thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) to determine the concentrations of volatile organic compounds (VOCs) in different school environments. The main objective of the study was to monitor VOCs in seven indoor and three outdoor environments at a school in Tarragona, Spain. However, in order to obtain more accurate information, it was necessary to determine the experimental diffusive uptake rates of the target VOCs in indoor settings through parallel passive and active sampling in one classroom. The results showed experimental diffusive uptake rates in the range of 0.38 mL min-1 and 0.95 mL min-1 with RSD % below 5% for up to 44 VOCs. The monitoring results showed that ethanol (23.84-83.16 µg m-3 ) and isopropyl alcohol (5.42-25.92 µg m-3 ) were the most common compounds found in indoor environments, with cleaning products as the main emission source. The VOCs i-pentane and n-pentane were found at the highest concentrations in the three sampling sites set in the school's playground, and their concentrations were strictly related to combustion processes from automobile traffic.