Abstract <p>The aim of this work is to study possibility of mechanochemical synthesis of polyaluminodiphenylsiloxanes. Dihenylsilanediol and aluminum tributoxide have been used for the first time for the synthesis under mechanical activation conditions. It has been found that the reaction results in aluminodiphenylsiloxanes with Si/Al ratio close to the prescribed value, while increase in activation time leads to the growth of rate of homocondensation process of initial dihenylsilanediol and, therefore, to increase in Si/Al ratio. It has been found by IR and NMR spectroscopy that aluminum atom forms with silanediol a polymeric aluminosiloxane chain with retention of butoxy groups. The obtained compounds have been shown to display considerably lower thermal stability than spatially branched metalloorganosiloxanes. The compounds prepared in the work have been characterized by the contemporary methods of analysis.</p>