This chapter is devoted to the use of flame atomic-emission and atomic-absorption spectrometry techniques to determine the stoichiometric composition, as well as studying the regularities of distribution of impurities and dopants in single crystals based on refractory oxides used as active media for solid-state lasers (leucosapphire, ruby, yttriumaluminium garnet), laser light modulators (strontium titanate), scintillation detectors (cadmium tungstate), solid electrolytes (┚-alumina), medical implants (leucosapphire). Growth of high quality single crystals requires not only adherence to specifications and the growing parameters but reliable methods of analytical control of their composition. Last years along with so-called F-centre forming elements, the increasing attention is given to alkali and alkali-earth impurities which also may cause worsening of quality of single crystals (Dobrovinskaya et al.,2007; Nagornaya et al., 2005; Tupitsyna et al., 2009). Digestion of refractory oxide single crystals is one of the most complicated and important stage of the procedure of analysis. Condensed phosphoric acid is recommended as an effective reagent for sample preparation of single crystals of oxide compounds. For the rapid flame spectrometry determination of alkali metals and calcium impurities, procedures of the sample preparation of water extracts of αand γ-forms of aluminum oxide, yttriumaluminum garnet and magnesium-aluminates used as raw materials for single crystals growing are proposed. It is also shown the effectiveness of ultrasonic sample preparation technique followed by the direct determination of Co and Ni in suspensions of α-Al2O3.