An assessment was carried out at a UK integrated steelworks to investigate the exposure of workers via inhalation to dioxins [polychlorinated dibenzo-p-dioxins (PCDD/F)], polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAH) including benzo[a]pyrene (B[a]P). Investigations focused on a basic oxygen steelmaking (BOS) plant and an iron ore sintering plant. The highest concentrations of PCDD/F and dioxin-like PCB were found at the BOS vessels and sinter strand area at the BOS and sinter plant, respectively. A risk assessment was carried out by comparing the daily intake of PCDD/F and PCB via inhalation with the recommended tolerable daily intake (TDI) proposed by the World Health Organisation (WHO). For the most exposed category of worker in this study (i.e. sinter plant workers inside the strand area), the estimated daily intake via inhalation was estimated to be 0.25 pg WHO-toxic equivalent concentrations (TEQ) kg−1 body weight (bw). Considering that the average UK adult exposure to PCDD/F from the diet is 1.8 pg WHO-TEQ kg−1 bw day−1, the results indicated that the estimated daily intake of PCDD/F and PCB via inhalation for sinter plant workers would not result in the recommended range of the TDI (1–4 pg WHO-TEQ kg−1 bw day−1) being exceeded. Cancer risks for a 40-year occupational exposure period were determined by multiplying the estimated intake by the inhalation cancer potency factor for 2,3,7,8-tetrachlorodibenzo-p-dioxin. For the most exposed category of worker, cancer risks from exposure to PCDD/F and PCB ranged from 2.5 × 10−6 to 5.2 × 10−5. Under most regulatory programmes, excess cancer risks between 1.0 × 10−6 and 1.0 × 10−4 indicate an acceptable range of cancer risk, suggesting a limited risk from PCDD/F and PCB exposure for workers in the sinter plant. With regard to PAH, B[a]P concentrations were typically <10 ng m−3 at all locations at both the sinter plant and the BOS plant. In several cases, particularly at the sinter plant, B[a]P concentrations were well below or only marginally above the target value of 1 ng m−3 specified in ambient air by the European Commission in the fourth ‘Daughter’ Directive of the Air Quality Framework Directive suggesting a very low risk of exposure for workers. For PAH, excess cancer risks ranged from 2.4 × 10−6 to 7.3 × 10−6 for BOS plant workers and from for 5.3 × 10−7 to 1.5 × 10−5 for sinter plant workers, well within the acceptable range proposed by the US EPA.