Polychlorodibenzo-p-dioxins, polychlorodibenzo-furans (PCDD/Fs) and dioxin-like polychlorobiphenyls (DL-PCBs) enter the food chain from the environment. In this study, we report the 2008–2018 time-trends in the PCDD/F and DL-PCB contamination of milk from buffaloes fed on local forage in rural areas of the Campania region. Validated according to QA/QC criteria, the dataset (N = 808 on a total of 2068 samples, after excluding follow-up results and outliers) was computed on the upper-bound value pg WHO-TEQ2005 g−1fat. We assessed time-trends and assayed baseline contamination levels, which displayed log-normal distribution. A significant decreasing trend (p < 0.01) was observed from 2008 to 2009 and 2010; the P50–P95 range fell from 2.37–8.48 pg WHO-TEQ2005 g−1fat (N = 393) in 2008 to 1.73–4.61 in 2009 (N = 86) and to 0.67–1.46 in 2010 (N = 42). From 2010 to 2018 (N = 329), no significant variation was found among years and the related dataset fitted a log-normal distribution (p < 0.05). Occurrence descriptors indicated that the baseline contamination of dairy products (mean = 0.54; P50–P95 = 0.47–1.24) in the Campania Region was well below the EU regulatory limit in force (5.5 pg WHO-TEQ2005 g−1fat). Given the Tolerable Weekly Intake of 2 pg WHO-TEQ kg−1 body weight (bw) proposed by the EFSA for PCDD/Fs and DL-PCBs, this level of baseline contamination is discussed with regard to the orientation of food safety and food security risk connected with buffalo mozzarella cheese production.