A new all-solid-state self-charging power cell (SCPC) has been fabricated using mesoporous PVDF-LiPF6 film as piezo-electrolyte. The solid piezo-electrolyte can act as both the electrolyte and piezo-separator, which is prepared through immobilizing the liquid electrolyte in mesoporous PVDF film. The all-solid-state flexible SCPC can be efficiently charged up by mechanical deformation, and thus can directly harvest/store the body-motion energy. The SCPC sealed in stainless-steel cell can be charged by compressive deformation (30N, 1Hz) and the storage capacity is 0.118μAh within 240s, which is about 5 times larger than that of the traditional non-integrated system. The SCPC sealed in flexible shell can be charged by the bending deformation. The all-solid-state flexible SCPCs can power a variety of wearable electronic devices, including sports bracelets, smart watches and LEDs. This work provides an innovative approach for developing new self-sustainable battery and self-powered wearable electronics.