Biomonitoring data of N,N-diethyl-meta-toluamide (DEET) in children is scarce and limited to controlled exposure and surveillance studies. We conducted a 24-hour observational exposure and human biomonitoring study designed to estimate use of and exposure to DEET-based insect repellents by Canadian children in an overnight summer camp setting. Here, we present our study design and methodology. In 2019, children between the ages of 7 and 13 took part in the study (n = 126). Children controlled their use of DEET-based insect repellents, and provided an account of their activities at camp that could impact insect repellent absorption. Children provided a total of 389 urine samples throughout the study day, and reported the time that they applied insect repellent, which allowed us to contextualize urinary DEET and metabolite concentrations with respect to the timing of insect repellent application. DEET (2.3% <Limits of detection (LOD)) and two metabolites, N,N-diethyl-m-(hydroxymethyl)benzamide (DHMB) (0% <LOD) and 3-diethylcarbamoyl benzoic acid (DCBA) (0% <LOD), were measured in urine samples. Three time difference scenarios were established for the data and analysed to account for these complex time-dependent data, which demonstrated the need for DEET biomonitoring to be done in context with the timing of a known DEET exposure or over the course of at least 14 to 24 hours to better capture the excretion curve. To our knowledge, this is the first field-based study of real-world exposure to DEET in children. Our experience and results suggest that this type of real-world observational exposure study with a human biomonitoring component can generate data reflective of actual exposure, but is not without significant logistic, practical, and analytical challenges.