Polyimide (PI) based on an aromatic backbone, is known as a high performance polymer. However its presenting extreme glass transition temperature and often insoluble in most organic solvents in fully imidized form. Various techniques have been extensively studied to overcome serious processing difficulties including incorporating flexible segmented or manipulate bulky side group into a rigid PI backbone and introduce an inorganic segment network into the PI matrix. However, the synthesis of PI containing silicone segments implanted through copolymerization and Sol-gel techniques have not been studied synergetic before and only published in separated paper. Recognising the importance of understanding the diversity of the nature of PI derived from the same monomer, it should be very interesting to systematically study two different methods, for obtaining an optimal performance of PI. The roles of silicone segment on the chemical stability, thermal, optical and electrical properties of PI systems were analyzed and structure properties relationship has been studied. Further this knowledge will be useful for the investigation to distinguish the properties of a PI system.