This study evaluated contamination by polychlorinated dibenzodioxins and dibenzofurans (PCDDs/Fs) and polychlorinated biphenyls (PCBs) in 390 feeds and 1756 food samples collected in Latium and Tuscany (Italy, 2016–2025) using HRGC-HRMS. PCDDs/Fs and dioxin-like PCBs (dl-PCBs) are expressed as WHO 2005 toxic equivalents (WHO₀₅-TEQ). Non-dioxin-like PCBs (ndl-PCBs) lack dioxin-like toxicity mechanisms due to their non-coplanar structure and are not assigned a toxic equivalence factor. Feed results were normalised to 12% moisture content. Median levels of WHO₀₅-PCDDs/Fs+dl-PCBs TEQ at the upper limit in feed were 10–100 times lower than those reported in European monitoring data (EFSA, 2002–2010) for comparable categories, including additives, premixtures, raw materials and compound feed, with plant and animal feed materials below 0.03 ng/kg and aquaculture feed at 0.24 ng/kg. Food contamination was generally low, with the median WHO₀₅-PCDDs/Fs+dl-PCBs TEQ 2–4 times lower than Italian national data (2013–2016), considering comparable categories such as meat, fish, milk, eggs, oils, baby foods, marine oils, animal fats and liver. Higher levels were observed in game meat, sheep products and fermented milk than in pork and poultry. The contamination remained stable over time. These results indicate an improvement in food safety thanks to national and EU regulations, although continued surveillance of high-risk and undersampled categories remains essential.