The invention provides a method for extracting rubidium and cesium from steel soot and/or volatile dust. The method comprises the steps that (1), the steel soot and/or volatile dust and a solvent aremixed to obtain a solution containing rubidium and cesium, purification is carried out through a purifying agent, and leach liquor containing rubidium and cesium is obtained; (2), an extracting agentis used for carrying out extracting on the leach liquor containing rubidium and cesium, rubidium and cesium in a load organic phase are stripped into water through an acidic material, and enrichment liquor is obtained; (3), the enrichment liquor is purified through the purifying agent, and purified enrichment liquor is obtained; and (4), extraction is carried out on the purified enrichment liquorthrough the extracting agent, the load organic phase is washed to remove rubidium through an aqueous solution, then cesium in the washed and rubidium-removed load organic phase is stripped into the aqueous phase through the acidic material, a cesium salt solution is obtained, and residual liquor after extraction and/or a washing water phase are/is a rubidium-rich solution. By means of the method,existing rubidium and cesium resource quantity is greatly expanded, a specific enrichment and purification technology is established, and significant economic value is achieved.