The development of multifunctional materials with optical and electrical properties has become a research hotspot in recent years. In this work, multifunctional 0.935(Bi${}_{0.5}$Na${}_{0.5}$)TiO₃–0.065BaTiO₃ (BNT–BT)-based ferroelectric ceramics doped with small amounts of CaMAlO₄ ($\mathrm{\text{M}}=\mathrm{\text{Dy}}$, Ho) were prepared, and the effect of CaMAlO₄ on the electrostrain and photoluminescence properties of the ceramics was studied. The results showed that the CaMAlO₄ addition weakened the ferroelectric properties of the BNT–BT matrix, and promoted the improvement of the electrostrain performance. For samples doped with 1.5$$mol% CaMAlO₄, the unipolar strain $S_{\mathrm{\text{uni}}}$ reached the largest values, which were 0.33% ($\mathrm{\text{M}}=\mathrm{\text{Dy}}$) and 0.38% ($\mathrm{\text{M}}=\mathrm{\text{Ho}}$) under an electric field of 70$$kV/cm, corresponding to a large signal $d_{33}^{?}$ ($S_{max}∕E_{max}$) of 471$$pm/V ($\mathrm{\text{M}}=\mathrm{\text{Dy}}$) and 543$$pm/V ($\mathrm{\text{M}}=\mathrm{\text{Ho}}$), respectively. In addition, due to the existing Dy${}^{3+}$ and Ho${}^{3+}$ luminescent ions, the modified samples exhibited excellent photoluminescence performance, which exhibited bright yellow emission ($\mathrm{\text{M}}=\mathrm{\text{Dy}}$) and green emission $(\mathrm{\text{M}}=\mathrm{\text{Ho}})$ under the blue excitation. Due to their multifunctional features, these materials have potential applications as “on-off” actuators, optical-electro integration and coupling devices.