The　construction　of　fine-grained　piezoceramics　with　large　transduction　coefficient　(d33 × g33)　and　mechanical　properties　is　the　key　to　the　development　of　high-quality　piezoelectric　energy　harvesters　(PEHs).　In　this　work,　samarium　doping　strategy　is　used　to　optimize　the　properties　of　Pb(Zn1/3Nb2/3)0.20(Zr1/2Ti1/2)0.80O3　(0.2PZN-0.8PZT)　piezoceramics.　The　results　show　that　Sm2O3　additive　can　effectively　refine　the　grain　size　accompanied　with　the　enhanced　mechanical　properties.　Meanwhile,　the　Sm2O3　addition　induced　the　formation　of　local　structural　heterogeneity　accompanied　by　the　reduced　domain　size,　which　boosts　the　transduction　coefficient.　A　cantilever　beam　type　PEH　was　further　assembled　from　the　preferred　samarium　modified　material,　and　the　power　density　was　up　to　489 μW/cm3　at　1 g　acceleration.　Excitingly,　its　relative　charging　ability　to　commercial　electrolytic　capacitor　has　a　relative　enhancement　of　~91%　compared　to　the　undoped　counterpart.　This　work　not　only　provides　a　piezoceramic　with　excellent　energy　harvesting　characteristics,　but　also　demonstrates　a　new　important　paradigm　for　the　development　of　fast-charging　microelectronic　storage　devices　in　wireless　sensor　networks.　©　2021　The　Authors.　International　Journal　of　Ceramic　Engineering　&　Science　published　by　Wiley　Periodicals　LLC　on　behalf　of　American　Ceramic　Society.