Silsesquioxane dendrimers offer versatile structural potential, prompting our innovative synthesis of G1 and G2 polyol dendritic systems with diverse silsesquioxane cores, ranging from mono-T8 to difunctional and tetrafunctional double-decker silsesquioxanes. Through a strategic combination of hydrosilylation and O-silylation reactions, we have formed an extensive compound library. A major focus was directed toward investigating the reaction conditions of G1.5 dendrimers, as well as evaluating the stability and reactivity of the novel -O-Me2Si-H group. Notably, we unveiled solubility trends of these synthesized dendritic systems in basic organic solvents, offering vital information for potential applications. Our work advances dendrimer research by unraveling intricate synthesis, reactivity, and properties. We contribute to the broader understanding of these organic-inorganic complex interactions and envisage diverse applications in multiple domains.