Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) are cancerogenic organic pollutants that priority controlled by Stockholm Convention with globally 182 signatories now. Secondary nonferrous smelting plants are confirmed to be important sources in China due to its large industrial activities and high emissions of PCDD/Fs. It is important to prioritize source to achieve source emission reduction by conducting field monitoring on typical case plants. Here, the emission profiles and levels of PCDD/Fs were investigated in 25 stack gas samples collected from three secondary copper production (SeCu), two secondary zinc production (SeZn) and two secondary lead production (SePb). Both average mass concentration and toxic equivalency quantity (TEQ) concentrations of PCDD/Fs all generally decreased in the order: SeCu > SeZn > SePb. It is noteworthy that the mean TEQ concentration in stack gas from SeCu with oxygen-enrich melting furnace technology, at 2.7 ng I-TEQ/Nm³, was much higher than the concentrations of other smelting processes. The average emission factors and annual release amounts of PCDD/Fs from SeCu, SePb and SeZn investigated were 28.4, 1.5, 10.4 μg I-TEQ/t and 1.03, 0.023, 0.17 g I-TEQ/year, respectively. The ratios of 2,3,7,8-TCDF to 1,2,3,7,8-PeCDF and OCDD to 1,2,3,7,8,9-HxCDD varied to large extent for three metal smelting, which could be used as diagnostic ratios of tracing specific PCDD/Fs sources. Addition of copper-containing sludge into the raw materials might lead to higher PCDD/Fs emissions. It is important to emphasize and reduce the PCDD/Fs emissions from oxygen-enrich melting furnace from secondary copper productions.