During 2015–2017, the atmospheric PM2.5, PM2.5/PM10, PCDD/Fs, PCDD/F phase distribution and PM2.5-bound total PCDD/Fs-WHO2005-TEQ content in Wuhu and Bengbu were investigated in this study. In addition, the sensitivity analysis for PM2.5-bound total PCDD/Fs-WHO2005-TEQ of Wuhu was also studied. During 2015–2017, the three-year average PM2.5 concentration in Wuhu was 53.0 µg m–3, and in Bengbu was 61.4 µg m–3; the results also showed the annual average PM2.5 concentrations of these two cities had declined, but the levels were still far above the WHO annual PM2.5 standard (10 µg m–3). In addition, in Wuhu, the PM2.5-bound total PCDD/Fs-WHO2005-TEQ contents in summer (0.166 ng-WHO2005-TEQ g–1) were approximately only 68.8% in magnitude lower than the average value of other three seasons (0.532 ng-WHO2005-TEQ g–1), and that of Bengbu in summer (0.187 ng-WHO2005-TEQ g–1) was approximately 66.7% in magnitude lower than the average value of other three seasons (0.561 ng-WHO2005-TEQ g–1). Sensitivity analysis showed that the PCDD/F concentration was the most positively correlated sensitive factor for PM2.5-bound total PCDD/Fs-WHO2005-TEQ, and when ΔP/P was changed from 0% to +50%, ΔS/S responded from 0% to +106%. The second positively correlated sensitive factor was PM10 concentration, and when ΔP/P was changed from 0% to +50%, ΔS/S responded from 0% to +72%. This was followed by atmospheric temperature, and its effect was negatively correlated, when ΔP/P was changed from –50% to +50%, ΔS/S responded from +73% to –112%. The last sensitive parameter was PM2.5 concentration, with the impact divided into two stages: when ΔP/P was changed from 0% to+70%, ΔS/S responded from 0% to +33%, but when ΔP/P was changed from +70% to +100%, ΔS/S responded from +33% to +25%.The results of this study provide useful information that can be used to achieve more insights into both atmospheric PM2.5 and PCDD/Fs.