This study investigates the concentrations of 17 PCDD/Fs and 12 dl-PCBs congeners in soil samples collected from industrial areas in Cartagena de Indias (Colombia) and Valencia (Spain). The aim is to assess the characteristic distribution patterns and the potential risk around cement plants within the selected locations, addressing the lack of data on PCDD/Fs and dl-PCBs in soils from the two studied areas. Soil samples were analysed using gas chromatography coupled to high-resolution mass spectrometry (GC-HRMS). The PCDD/Fs concentrations varied from 0.01 pg g−1 dw to 520.43 pg g−1 dw in Colombia and from 0.01 pg g−1 dw to 150.48 pg g−1 dw in Spain. For dl-PCBs, levels ranged from 0.03 pg g−1 dw to 1611.83 pg g−1 dw in Colombia and from 0.06 to 189.64 pg g−1 dw in Spain. Despite the differences observed in concentration terms between the two areas studied, the same pattern of congeners was observed. The hazard index (HI) values for exposure of adults and children in soil were, in overall, smaller than one (HI < 1), while the total cancer risk (TCR) values exceeded the acceptable risk value of 10−6, which indicate probable non-carcinogenic and carcinogenic risks resulting from exposure to PCDD/Fs and dl-PCBs in these areas. The ecological risk was assessed using the Contamination Factor (CF) and the Ecological Risk Index (ERI), revealing significant contamination in the studied areas.