The aim of this article is to improve the interfacial adhesion between silicone rubber (SR) and Rayon fiber by the help of functional hybrid POSS nanoparticles. Two POSS types were compared, octavinyl-POSS (O-POSS) and methacryl-POSS (M-POSS), having reactive -C(sic)C- double bonds that can impart in peroxide crosslinking. O-POSS is nonpolar, whereas M-POSS is polar and is able to make H-bond with Rayon fibers. POSS type and their concentrations were examined as the experimental parameters. H-adhesion tests indicated that both POSS types enhanced the adhesion of SR composites to Rayon fibers compared with control recipe. Specifically, slightly higher values were obtained with the use of M-POSS. It was observed that both O-POSS and M-POSS slowed down the curing rate but increased the degree of crosslinking. The cure extent of O-POSS containing composites was found to be higher than that of M-POSS containing ones. Thermal gravimetric analyses revealed that thermal stability of SR composites was significantly improved by the addition of POSS particles. Higher char yield and degradation temperatures were obtained with O-POSS at higher loadings with respect to M-POSS. The POSS distribution at lower loading levels was found to be homogenous for both POSS types as observed from scanning electron microscope and transmission electron microscope.