Transparent　dielectric　ceramics　are　splendid　candidates　for　transparent　pulse　capacitors　(TPCs)　due　to　splendid　cycle　stability　and　large　power　density.　However,　the　performance　and　service　life　of　TPCs　at　present　are　threatened　by　overheating　damage　caused　by　dielectric　loss.　Here,　a　cooperative　optimization　strategy　of　microstructure　control　and　superparaelectric　regional　regulation　is　proposed　to　simultaneously　achieve　excellent　energy　storage　performance　and　real‐time　temperature　monitoring　function　in　NaNbO3‐based　ceramics.　By　introducing　aliovalent　ions　and　oxides　with　large　bandgap　energy,　the　size　of　polar　nanoregions　is　continuously　reduced.　Due　to　the　combined　effect　of　increased　relaxor　behavior　and　fine　grains,　excellent　comprehensive　performances　are　obtained　through　doping　appropriate　amounts　of　Bi,　Yb,　Tm,　and　Zr,　Ta,　Hf　in　A‐　and　B‐sites　of　the　NaNbO3　matrix,　including　recoverable　energy　storage　density　(5.39 J cm−3),　extremely　high　energy　storage　efficiency　(91.97%),　ultra‐fast　discharge　time　(29 ns),　and　superior　optical　transmittance　(≈47.5%　at　736 nm).　Additionally,　the　phenomenon　of　abnormal　fluorescent　negative　thermal　expansion　is　realized　due　to　activation　mechanism　of　surface　phonon　at　high　temperatures　that　can　promote　the　formation　of　[Yb···O]‐Tm3+　pairs,　showing　great　potential　in　real‐time　temperature　monitoring　of　TPCs.　This　research　provides　ideas　for　developing　electronic　devices　with　multiple　functionalities.