Due　to　the　self-supplied　energy　requirements　of　wearable　electronic　devices,　flexible　piezoelectric　energy　harvesters　(FPEHs)　that　can　convert　the　vibration　energy　in　the　environment　into　electrical　energy　have　received　widespread　attention　in　recent　years.　The　key　to　increasing　the　power　generation　capacity　of　FPEHs　is　to　increase　the　piezoelectric　charge　constant　d(33)　while　reducing　the　internal　resistance,　which　is　still　a　huge　challenge　for　ceramic/polymer　composites.　In　this　work,　a　synergistic　effect　is　used　to　construct　FPEHs　with　high　power　generating　capacity.　On　the　one　hand,　a　highly　electroactive　0.2Pb(Zn1/3Nb2/3)O-3-0.8Pb(Zr1/2Ti1/2)O-3　(PZN-PZT)　ceramic　skeleton　is　constructed　through　a　freeze-casting　method　to　greatly　increase　the　d(33)　of　a　PDMS　based　composite.　On　the　other　hand,　multi-walled　carbon　nanotubes　(MW-CNTs)　are　introduced　as　a　bridging　phase　to　reduce　the　internal　resistance　of　the　composite.　The　2-2　type　PZN-PZT/MW-CNTs/PDMS　piezocomposite　prepared　using　this　strategy　has　a　d(33)　as　high　as　144　pC　N-1,　which　is　significantly　better　than　those　of　previously　reported　composites.　The　FPEH　with　dimensions　of　1.5　x　1.5　x　0.1　cm(3)　can　light　22　LEDs　through　the　rectifier　circuit　without　any　storage　units,　showing　an　important　application　prospect　for　self-supply　of　energy　in　wearable　electronic　devices.