The invention relates to a method of separating and extracting rubidium and cesium from coal. The method comprises the following steps of: smashing coal; dissolving the smashed coal in a mixed acid to filter; extracting a filtrate and then adding iodine chloride to generate a precipitate; then adding the precipitate into potassium iodide to be dissolved to generate rubidium chloride, cesium chloride, potassium chloride and iodine single element; extracting the iodine single element with an organic solvent; then extracting the solution containing rubidium chloride, cesium chloride and potassium chloride with t-BAMBP to generate a precipitate; then dissolving the precipitate in diluted hydrochloric acid; then performing evaporative crystallization; and finally obtaining high purity rubidium chloride and cesium chloride. The method of separating and extracting rubidium and cesium from coal provided by the invention separates and extracts rubidium ions and cesium ions from coal by means of a method of precipitation, extraction and counter-extraction, so that the process step of separating rubidium and cesium from coal is simplified, and the production cost is low and the production period is short.