A series of soluble polyhedral oligomeric silsesquioxane (POSS) based inorganic-organic hybrid nonlinear optical materials with different architectures, such as dumbbell-type, bead-type and network-type structure, were prepared based on the hydrosilylation addition reaction of multifunctional octahydridosilsesquioxane (T-8(H)) with different azobenzene chromophore monomers. These resultant hybrid composites arc soluble in common organic solvents such as tetrahydrofuran, toluene, and chloroform, and exhibit good film-forming ability. Their structures and properties were characterized and evaluated with IR, H-1 NMR, Si-29 NMR, TGA, DSC, optical limiting measurement and Z-scan technique, respectively. The results show that the structure of these resultant. hybrids can be effectively tuned by simply varying the feed ratio and molecular structure of organic chromophore monomers. The incorporation of inorganic POSS into organic azobenzene chromophore has endowed the hybrids with well optical limiting properties and high thermal stability. Simultaneously, the relationship between molecular structure and properties of these hybrids were investigated in detail.