End-of-life vehicles and e-waste contain several hazardous substances that can contaminate the environment during treatment processes. Occurrences and adverse effects of toxic organic pollutants emitted from 3 shredder plants located in Wallonia, Belgium, were investigated by chemical and biological analyses of fluff, dust, and scrubbing sludge sampled in 2019. Site 1 showed the highest concentrations of chlorinated compounds in sludge with 7.5 ng/g polychlorinated dibenzo-dioxins/furans and 84.5 µg/g estimated total polychlorinated biphenyls, while site 3 led the brominated flame retardant levels in dust (53.4 µg/g). The level of polycyclic aromatic hydrocarbons was highest in the sludge samples, 78 and 71 µg/g for sites 2 and 3, respectively. The samples induced significant dioxin-like activities in murine and human cells at concentrations of around 0.01–0.1 and 0.5–1 ng (sample) per ml (medium), respectively, with the efficacy similar to 2,3,7,8-tetrachlorodibenzodioxin and EC50 values of around 1 and 10 ng/ml. The samples also displayed high estrogenic activities, already at 1 ng/ml, and several induced a response as efficient as 17β-estradiol, albeit a low androgenic activity. Shredder workers were estimated to be highly exposed to dioxin-like compounds through dust ingestion and dermal absorption, which is of concern.