Inorganic luminescent materials based on photoluminescence (PL) and thermoluminescence (TL) display considerable potential applications for optical anti-counterfeiting devices. Ca2-xNb2O7:xPr(3+) (x = 0.00075, 0.001, 0.002, 0.003, 0.004) ferroelectric ceramics have been fabricated. The basic crystal structure, local ferroelectricity and PL/TL properties of the ceramics have been investigated in this study. The PFM measurement proves that the grains in the prepared ceramics are monodomain state. Furthermore, the synthesized phosphors are embedded into polydimethylsiloxane (PDMS) matrix to fabricate a novel optothermal responsive device with high elasticity, transmittance and heat resistance. The PL and TL photographs of the designed device further demonstrate that the device is promising in practical applications such as optical anti-counterfeiting and information storage.