The present study reports on the use of three types of polyhedral oligomeric silsesquioxanes (POSS) nanoparticles with various organic substituents as fillers in a fluoroelastomer (FKM). A series of/POSS elastomer composite thin films is prepared. Microstructural SEM/TEM (scanning electron microscopy/transmission electron microscopy) imaging reveals a dispersion state allowing the presence of micron-sized domains. The influence of POSS content is studied in order to optimize thermal stability and mechanical properties of the composite thin films. Both POSS-A (with an acryloyl functional group and seven isobutyl substituents) and POSS-P (with eight phenyl substituents) lead to higher thermal stability and modulus of the composites, with respect to the unfilled FKM terpolymer matrix. covalent grafting of POSS-A onto the FKM network is found to play a critical role. Enhanced storage modulus in the rubbery plateau region (+210% at 200 °C for 20 phr) suggests that POSS-A is particularly suitable for high temperature applications.