Tongling and Nanling region is abundant in copper ore resources. From the 1980s, a large number of the sites of mining and smelting have been found in this region, the earliest of which could date back to the Erlitou period. Slags, furnace walls and other smelting remains from the sites of mining and smelting provided a good deal of archaeological materials for the study of the smelting technology of copper ore in ancient China. Slag samples collected from the smelting sites in Tongling and Nanling region, Anhui Province were analyzed by means of X-ray diffractometer (XRD), X-ray fluorescence spectrometer (XRF) and scanning electron microscope with energy-dispersive X-ray spectrometer (SEM-EDS) to understand the smelting process of copper ore. The results of XRD showed that the main phase compositions in the slag samples included fayalite, augite and hedenbergite, accompanied with quartz, cristobalite and magnetite, et al., which corresponded with the phase characteristics of copper smelting slag. From the contents of SiO2, CaO and Fe2O3, all slag samples were divided into three groups: Type Ⅰ, Type Ⅱ and Type Ⅲ. The Type Ⅰ was Iron-Silicon-Calcium slag, which was high in the contents of calcium, iron and silicon. The calcium contents of the Type Ⅰ slag were much higher than those of the TypeⅡ and the Type Ⅲ slag. The Type Ⅱ was iron-rich slag, and its Fe2O3 contents were higher than those of the Type Ⅰand the Type Ⅲ slags. The Type Ⅲ was silicon-rich slag which was higher in SiO2 contents and lower in the calcium and iron contents. The Fe2O3 contentsin all slags were higher than the common melting slags. Combined with the results of XRD, it was concluded that all slag samples are from the smelting process of copper ores. Calcium and iron levels in the Type Ⅰ and Type Ⅱ slags vary obviously and show the significant negative correlation, which indicated that calcium and iron in the slags was not controlled artificially and it is very possible that the calcium and iron in the slags were from the copper ores. Based on the contents of calcium and iron, it could be inferred that the early craftsmen in the Tongling and Nanling region didn’t seem to understand the effects of calcium-bearing flux and iron-bearing flux and master the technology of matching ore of different kinds of copper ore. According to the results of SEM-EDS, the metal prills in the slags mainly included matte, copper and arsenic bronze, which showed that the smelting activities of copper and arsenic bronze coexisted in Tongling and Nanling area. The matte prills in the slags were mainly from different sites of mining and smelting, and the matte prills with the increasing copper content in turn were not extensively found in the same sites of mining and smelting. Therefore it was difficult to certify the existence of the matte smelting process, and it was not verified whether the smelting process of “copper sulfide ore-matte-copper” has been widely used in this area in the Pre-Qin Period. The matte prills in this work were possibly produced by the dead roasting process of copper sulfide ores or cosmelting process of the copper sulfide-oxide ore. On the basis of the arsenic bronze prills in the slag of Xiajiadun site, we could draw a conclusion perhaps that the ancient craftsman in this area mastered the cosmelting technology of arsenic copper in the Western Zhou period. The research results have an important significance for the study on the origin, the development and production mode of early smelting process in ancient China.