A simple and elegant extractive separation method for trace level rubidium has been developed using dibenzo-24-crown-8 from picric acid medium. Rubidium was quantitatively extracted from 0.0006 – 0.05 M picric acid with 0.0006 – 0.01 M dibenzo-24-crown-8 in nitrobenzene as a diluent. From the organic phase rubidium was quantitatively stripped with 1–10 M HNO3, 1–8 M HBr, 0.5–10 M HCl and 10 M HClO4. Rubidium was estimated by flame emission spectroscopy at 780 nm. Separation of rubidium was carried out from number of binary mixtures. Most of the elements from s-block, p-block & d-block showed high tolerance limits. It was possible to separate rubidium from associated elements in multicomponent mixtures. The method was extended for the determination of rubidium in various rock samples.