A novel all-polymeric material with high dielectric constant (k) has been developed by blending poly (vinylidene fluoride) (PVDF) with polyamide-6 (PA6). The dependence of the dielectric properties on frequency and polymer volume fraction was investigated. When the volume fraction of PA6 is 20%, the dielectric property is better than others. The SEM investigations suggest that the enhanced dielectric behavior originates from significant interfacial interactions of polymer-polymer. The XRD demonstrate that the PA6 and PVDF affect the crystalline behavior of each component. Furthermore, the stable dielectric constants of the blends could be tuned by adjusting the content of the polymers. The created high-k all-polymeric blends represent a novel type of material that are simple technology and easy to process, and is of relatively high dielectric constant, applications as flexible electronics.