From 2015 to 2017, the atmospheric PM2.5, the total PCDD/Fs-WHO2005-TEQ concentrations, PM2.5-bound total PCDD/Fs-WHO2005-TEQ contents, and the gas-particle partitioning of PCDD/Fs in Handan and Kaifeng were investigated. In addition, a regression analysis of the air quality index (AQI) and total PCDD/Fs-WHO2005-TEQ concentration was also studied. From 2015-2017, in Handan, the three-year average PM2.5 concentrations in spring, summer, autumn and winter were 66.9, 61.3, 74.8, and 138 µg m–3, respectively and averaged 85.3 µg m–3, which was 1.2 orders of magnitude higher than that in Kaifeng (71.1 µg m–3). The three-year average PM2.5-bound total PCDD/Fs-WHO2005-TEQ content in spring, summer, autumn, and winter in Handan were 0.88, 0.28, 0.67, and 0.72 ng WHO2005-TEQ g–1, respectively, and averaged 0.64 ng WHO2005-TEQ g–1, which was 1.1 order of magnitude higher than that in Kaifeng (0.57 ng WHO2005-TEQ g–1). The three-year average fraction of gas phase total PCDD/Fs-WHO2005-TEQ concentrations in spring, summer, autumn, and winter in Handan were 26.4%, 62.8%, 28.9%, and 3.34%, respectively, and averaged 30.4%. The three-year average fraction of gas phase total PCDD/Fs-WHO2005-TEQ concentrations in Kaifeng (34.3%) was 1.1 order of magnitude higher than that in Handan (30.4%). Positive correlations between the AQI and the total PCDD/Fs-WHO2005-TEQ concentration were found and their R2 values in 2015, 2016, and 2017 were 0.929, 0.921, and 0.876, respectively. Therefore, the AQI can be used to roughly predict the level of total PCDD/Fs-WHO2005-TEQ in ambient air through the use of a regression equation in these two cities.