A novel fluorinated amine compound prepared was characterized by 1H NMR, 19F NMR and FTIR. Subsequently, polymerized with pyromellitic dianhydride results in the formation of neat fluorinated polyimide matrix (PI). In addition, three different nanomaterials such as of graphene oxide (GO), Octa (aminophenyl) silsesquioxane (OAPS) and graphene oxide blended with Octa (aminophenyl) silsesquioxane (GO-OAPS) were reinforced separately with PI in varying weight percentages. The developed composites were studied for their thermal, dielectric and hydrophobic behaviour and compared. Comparatively the 7% OAPS-GO/PI exhibits lower dielectric constant (k = 2.1) than that of neat PI, GO/PI and OAPS/PI composites. The OAPS grafted onto the GO surface contributes for lower polarity due to its porous caged structure and contributes for higher insulation behaviour. Further, the 7% OAPS-GO/PI also exhibits higher contact angle (107°) due to the less polar nature of the composites which in turn contributes to enhanced hydrophobic behaviour. The data obtained from morphological, surface and dielectric studies indicate that the OAPS-GO/PI composites exhibited substantially improved hydrophobic and dielectric properties than that of GO/PI and OAPS/PI.