New stable and adherent coating materials have been synthesized on the basis of inorganic/organic hybrid polymers. As the inorganic part, different poly (silsesquioxanes) (PSSQ) have been functionalized to act as polymeric chain transfer agents (CTAs) for a reversible addition fragmentation chain transfer polymerization, thereby determining the starting point of a controlled radical polymerization of vinyl-type monomers. Using two different CTAs acrylates, we have successfully polymerized methacrylates and styrene under RAFT polymerization conditions. Different monomers were copolymerized in such an organic block to incorporate multiple functionalities. The variation of the block ratios and the secondary condensation behavior of the inorganic block were investigated. Finally, these materials were used as surface coating materials on silicon, glass, metal, and polymeric substrates. Successful surface functionalization was demonstrated by contact angle measurements. The stability of the film and the adhesion on the substrate were tested in an ISO tape test.