Herein, we report an efficient synthesis and functionalization of trifunctional open-cage-type silsesquioxanes. The method proposed has been successfully applied for the synthesis of a library of incompletely condensed silsesquioxanes with vinyldiorganosilyl functional groups, which allows further modification. Detailed studies of hydrosilylation of sterically different open-cage vinylsilsesquioxanes with a wide spectrum of phenylsilanes catalyzed by platinum and rhodium compounds are also reported. The influence of the reaction parameters, types of reagents, and catalysts employed on the efficiency of the process was examined. Optimization of the process based on the above results permitted the design of a very attractive method for the synthesis of multifunctionalized silsesquioxanes with excellent yields and regioselectivity. Moreover, the results allowed the choice of the most efficient catalyst whose application led to the selective formation of substituted open-cage silsesquioxanes. These new compounds have been fully characterized and studied in terms of their thermal properties.