<p>The scientific community has not yet addressed the study of indoor and urban outdoor PCBs associated with airborne particulate matter. PM₁₀ particles were collected simultaneously across a year in an urban outdoor and indoor environment, ulteriorly extracting and quantifying 11 PCBs using ASE and GC/MS, respectively. Outdoor and indoor annual average PM₁₀-bound ƩPCBs levels were 599.13 and 628.13 pg/m³, with the highest and lowest contributions from congeners with lower molecular weight (PCB 31 and 49) and higher molecular weight (PCB 183 and 194). Outstanding monthly, seasonal, and annual outdoor vs. indoor correlations were observed, sustaining similar pollution profiles at both locations along the study and marking higher polluting levels in the cold than warm periods. Outdoor PCBs 31, 99, 149, and 151 were appointed as the more representative, while PCBs 49 and 110 for the indoor air. Mathematical expressions estimating monthly total PCBs concentration in the function of the more representative monthly congeners were formulated, facilizing monthly accumulated exposure assessment in limited resources scenarios, which is primordial in public health. Annual average I/O ratios were higher or equal to 1 for all target pollutants, mainly from December 2017 to January 2018. Individually, the outdoor and indoor CR values were below the Limit value, including the continuous exposure approach, where the analyzed PCBs ranged from 10⁻⁵ to 10⁻⁶ at all seasons. This study provides pioneer information on a scientific topic that has not been assessed, helping urban air quality management and offering clues to other cities.</p>