Non-functional derivatives of polymethylsilsesquioxane (PMSSQ) dendrimers of first to fourth generation were synthesized for the first time using combination of divergent and convergent synthetic approaches. Obtaining of non-functional derivatives allowed investigating their properties not only in solution, but also in the bulk. While having practically identical chemical composition with linear polydimethylsiloxanes, PMSSQ dendrimers demonstrated increased density, a significant increase in the viscous flow energy, an absence of crystallization, and a gradual increase in the glass transition temperature with the generation.