A self-charging power cell (SCPC) is a structure that hybridizes the mechanisms for energy conversion and storage into one process through which mechanical energy can be directly converted into electrochemical energy. A key structure of an SCPC is the use of a polyvinylidene fluoride (PVDF) piezo-separator. Herein, we have fabricated a piezoelectric β-form PVDF separator with a highly porous architecture by introducing ZnO particles. The electrochemical charge/discharge performance of this SCPC was greatly enhanced at lower discharge rates compared to highly stretched (high-β-content) or less porous PVDF membranes. The lower charge-transfer resistance of this well-developed porous piezo-separator is the main factor that facilitated the transport of Li+ ions without sacrificing piezoelectric performance. This study reveals a novel approach for improving the performance of SCPCs.