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New type of star-shaped polydimethylsiloxanes based on 8-, 12- and 24-membered stereoregular cyclosiloxanes and octasilsesquioxane as a core and polydimethylsioxane chains of different length as beams have been obtained and fully characterized by IR- and NMR-spectroscopy, GPC, DSC, TGA. The DSC study has shown that the introduction of the stereoregular cyclosiloxanes or octasilsesquioxane as a core to structure of polydimethylsiloxanes exerts considerable impact on their thermophysical properties.