Among the organic dielectrics, polyvinylidene fluoride PVDF-based polymers present the highest level of polarizability with permittivity >35. Nonetheless, their applications in advanced electronics and industrial uses are limited by significant leakage current under high voltage, which is considered the principal cause of device energy consumption and short lifetime. Therefore, the main objective of this paper was to focus on alternative capacitor structure-based polyvinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene (PVDF-TrFE-CTFE) terpolymers to efficiently limit the leakage current and lead to enhanced electrical breakdown with negligible degradation of polarization level. The novel bilayer capacitor was constructed by depositing a thin barrier layer of high polar PVDF-HFP copolymer on the terpolymer via a rapid solution-casting technique. The relationship between leakage current, dielectric strength and conduction mechanisms was investigated. Implementation of such a barrier layer led to a significant reduction (70%) in leakage current and ferroelectric losses (approximately 90%), thus boosting the performance of multilayered material up to 50% of enhanced energy-storage efficiency. Experimental results are very promising, allowing to confirm that combining both terpolymer and copolymer in a hybrid multilayer design makes a possibility to achieve the best compromise in terms of energy efficiency, dielectric properties, and breakdown strength.