The growth kinetics of Ce(IV)-O-containing layers produced by ionic layering were studied as a function of the concentration and pH of the reaction solutions and rinsing liquids, process duration, and number of layering cycles. Conditions were established for the formation of nanolayers through chemical reactions in the adsorption layer. The layers were characterized by UV/visible and Fourier-transform IR spectroscopies, x-ray photoelectron spectroscopy, chemical analysis, and ellipsometry. The results indicate the formation of cerium(IV) hydroperoxide layers. The layer thickness can be controlled to within 1 nm by adjusting the number of layering cycles. The effect of heating in air on the composition of the layers was examined. Using the same conditions as in the synthesis of the Ce(IV)-O-containing layers, Ce(IV)-La-O-containing layers were synthesized.