A RNAA method has been developed for the simultaneous determination of Rb and Cs in geological samples. The method is based on precipitation with sodium tetraphenylborate followed by NaI(Tl) gamma spectrometry. Three mica dust particulate samples and two USGS standard rocks, BCR-1 and W-1 were analyzed. Dipicrylamine (DPA) and 2-thenoyl-trifluoroacetone (TTA) in nitrobenzene were also used for solvent extraction. The precipitation method is better than solvent extraction.