The invention relates to a technology of extracting and separating valuable metals such as Pb, In, Sb, Cu and Sn from lead smelting converter slags, comprising the following steps: adding carbonaceous reducing agent in raw materials which are produced in the process of crude lead smelting and contain Pb, In, Sb, Cu and Sn; smelting the raw materials and the carbonaceous reducing agent in an electric furnace or a reverberatory at the temperature over 1000 DEG C, reducing the Pb, Cu, Sb, Sn, In and the like into metals and forming alloy, sorting out silicon and other components as slags; mixing sodium hudroxide with weight accounting for 40-60% of the alloy weight into the alloy, adding oxidizer and copper removal agent with weight accounting for 5-20% of the alloy weight, oxidizing the In, Sn, Sb and Cu for slagging and extracting the metallic lead; washing oxidizing slags to extract Sn, neutralizing the Sn by adding acid through washing water, regulating pH value to 3-4 and obtaining tin slags; obtaining stibium slags after acid leaching and separating of washing slags; obtaining copper sponge by replacement with ferrous powder by pickle liquor; extracting indium from replaced liquid and extracting organic phase by adopting TBP+octanol+karaffin oil, with extraction phase ratio of O / A equal to 1:1. The direct yield and recovery rate of metallic In, Pb, Sn and Sb are respectively over 90% and 95%.