The occurrence of organochlorine pesticides (OCPs) used decades ago for vector control in urban areas is still reported as a threat to human health. Pyrethroids emerged as a replacement for OCPs in sanitary campaigns and are currently the main insecticides used for vector control worldwide, with prominent use as agricultural and household insecticides, for veterinary and gardening purposes, and as wood preservative. This study aimed to assess the occurrence, seasonal variation, and potential sources of pyrethroids in ambient air of two urban regions of Southeastern Brazil, along with the potential health risks to local populations via inhalation exposure. Pyrethroids were sampled by polyurethane foam passive air samplers and their concentrations were determined by gas chromatography coupled with electron capture negative ionization mass spectrometry (GC/ECNI-MS). Atmospheric pyrethroid concentrations (hereinafter reported in pg m−3) were considerably higher than those reported by previous studies worldwide. Cypermethrin (median: 2446; range: 461–15 125) and permethrin (655; 19–10 328) accounted for 95% of the total measured pyrethroids in ambient air. The remaining fraction comprised smaller amounts of bifenthrin (46; urban-industrial > background areas. HQs increased with decreasing age group, but deterministic and probabilistic estimates did not identify direct health risks for any group. Nevertheless, since only inhalation exposure was considered in this work, other pathways should be investigated to provide a more comprehensive risk assessment of the human exposure to pyrethroids.