Five secondary aluminum metallurgy enterprises in the southwest area of China were measured for emissions of PCDD/Fs. The results indicated that the emission levels of PCDD/Fs (as TEQ) were 0.015-0.16 ng x m(-3), and the average was 0.093 ng x m(-3) from secondary aluminum metallurgy enterprises. Emission factors of PCDD/Fs (as TEQ) from the five secondary aluminum metallurgy enterprises varied between 0.041 and 4.68 microg x t(-1) aluminum, and the average was 2.01 microg x t(-1) aluminum; among them, PCDD/Fs emission factors from the crucible smelting furnace was the highest. Congener distribution of PCDD/F in stack gas from the five secondary aluminum metallurgies was very different from each other. Moreover, the R(PCDF/PCDD) was the lowest in the enterprise which was installed only with bag filters; the R(PCDF/PCDD) were 3.8-12.6 (the average, 7.7) in the others which were installed with water scrubbers. The results above indicated that the mechanism of PCDD/Fs formation was related to the types of exhaust gas treatment device. The results of this study can provide technical support for the formulation of PCDD/Fs emission standards and the best available techniques in the secondary aluminum metallurgy industry.