The present work derives a relationship between structure and properties of hydrogenated nitrile rubber (HNBR) in the presence as well as absence of nanofillers. Four different grades of HNBR were selected to examine the influence of polarity, unsaturation, and molecular weight on thermal, mechanical, and dynamic mechanical properties of the elastomers and particularly their nanocomposites. An increase in thermal stability, tensile strength, modulus at 100% elongation as well as storage modulus of the unfilled rubber was observed with increase in polarity (acrylonitrile content). Different nanofillers, such as montmorillonite, sepiolite, and nanosilica were used to improve the above properties of the unfilled rubber. Interestingly, a reverse trend of thermal properties was observed for the nanocomposites with acrylonitrile variation, although mechanical and dynamic mechanical properties exhibited similar trend to those of the unfilled rubber. These properties, however, gradually deteriorated as the level of unsaturation on the polymer backbone was increased. On addition of the nanofillers, it was found that the improvement in thermal and mechanical properties was higher for the elastomer having 5.5% diene content. The results were explained by X-ray Diffraction, Atomic Force Microscopy, Energy Dispersive X-ray mapping, and swelling studies. POLYM. ENG. SCI., 50:1389-1399, 2010. (C) 2010 Society of Plastics Engineers