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Pesticides are environmental contaminants of great interest because of their toxicity, persistence in the environment and bio-accumulative nature. However, there is a scarcity of literature concerning human exposure to pesticides through the consumption of contaminated drinking water. This study investigates the levels of multiple pesticides in drinking water and their subsequent carcinogenic and non-carcinogenic risk in five selected districts (Peshawar basin) of Khyber Pakhtunkhwa-Pakistan, to understand the exact scenario of pesticide toxicity in the sources of drinking water. The water samples were extracted by liquid–liquid extraction and analyzed using gas chromatography mass spectrometry (GCMS). Results obtained indicated that the detected concentrations of ∑21 pesticides ranged between 0 and 883.7 µg L−1 in the study area. The highest concentration was detected for methiocarb (mean 5.30 µg L−1), followed by acetamiprid (0.90 µg L−1), while the lowest was observed for cyhalothrin (0.01 µg L−1). The highest concentration of EU Watch List of Contaminants of Emerging Concern (methiocarb and acetamiprid) in the study area is alarming. Most of the pesticide residues recorded in the water samples exceeded the maximum residue limits except for dieldrin and cyhalothrin. Whereas, the residues of aldicarb, carbofuran deg, carbofuran, atrazine, alpha endosulfan, beta endosulfan, cypermethrin-1, difenoconazol-I and difenoconazol-II were not observed in any of the collected samples. The incremental lifetime cancer risk of endocrine disruptors such as dieldrin, o,p′ DDT, o,p′ DDD, and p,p′ DDE was > 10–6, posing potentially serious carcinogenic risk to the local inhabitants. Whereas, the non-carcinogenic risk through pesticide exposure was negligible, suggesting no/little risk to the inhabitants from these chemicals in drinking water. Regular monitoring is needed to evaluate pesticide concentrations not only in drinking water sources but also in soil and food crops as they pose serious eco-toxicological risks. [ABSTRACT FROM AUTHOR]