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 realātime temperature monitoring function in NaNbO3ābased 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 Aā and Bāsites of the NaNbO3 matrix, including recoverable energy storage density (5.39Ā JĀ cmā3), extremely high energy storage efficiency (91.97%), ultraāfast discharge time (29Ā ns), and superior optical transmittance (ā47.5% at 736Ā 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 [YbĀ·Ā·Ā·O]āTm3+ pairs, showing great potential in realātime temperature monitoring of TPCs. This research provides ideas for developing electronic devices with multiple functionalities.