Antiferroelectric (AFE) Pb0.96La0.04Zr0.90Ti0.10O3 (PLZT) and AgNbO3 (AN) ceramics were fabricated codoped with 1 mol% Er and various contents of Yb3+ ions. The ceramics exhibit good energy storage performances and electric‐field‐controlled photoluminescence (E‐PL) intensity modulations, both of which are attributed to the reversible AFE‐ferroelectric phase transition that accompanies a structural evolution. Accordingly, a noncontact energy charge/discharge monitor is proposed based on the E‐PL effect, which is convenient and safe for the high‐energy density capacitors. Besides, the PLZT and AN ceramics exhibit opposite E‐PL behaviors that are caused due to different crystal space group transitions.