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Charge transport plays very important role in many electronic materials. Recently, making use of the delocalized electrons in conjugated π-electrons in organics, several all-polymer composites have been developed which exhibited dielectric constant higher than 1,000 and high electromechanical responses with much reduced electric field (for example, 14% strain induced under 25 MV/m with an elastic energy density of 0.85 J/cm3). This talk will discuss these developments, including the significant enhancement of the dielectric and electromechanical responses in these composites when the inclusion size is reduced from sub-microns to nanometers. The interfacial polarization exchange effect and local field fluctuations in these nano-composites play very important role in enhancing the dielectric and electromechanical responses.