The interaction of magnesium carbonate with polyphenylsiloxane under the conditions of mechanochemical activation with subsequent heating has been investigated. Based on the TGA and DTA data, it has been shown that, upon heating up to 420°C, the reaction proceeded completely with the release of carbon dioxide. The polymer was dissolved in DMFA and purified by repeated precipitation with water. The polymer yield was 64%. The residue insoluble in organic solvents has been obtained by evaporation of an aqueous solution. The composition and structure of the synthesis products have been analyzed by means of element analysis, IR spectroscopy, and diffractometry. It has been demonstrated that the fraction soluble in DMFA had a silicon-to-magnesium ratio equal to 4.2, while the fraction isolated from water had this ratio equal to 1.0. The IR and XRD data enabled one to conclude that, regardless of the different compositions, the structures of all fractions were similar and corresponded to mesomorphic layered polymers produced by the ion exchange method.