Eu3+-doped sodium tantalum phosphate glass-ceramics containing bronze -like perovskite crystalline phase Na2Ta8O21 were obtained with different crystalline states (degree of crystallinity and average crystallite size) by a suitable control of the heat-treatment time and temperature of the precursor glass. Luminescence properties of Eu3+ in these materials are in agreement with a progressive insertion of the rare earth ions in the sodium tantalate Na2Ta8O21 phase, as probed by a clear decrease of the intensity ratio between transitions [5D0 →] 7F2/7F1 and narrowing of characteristic emission bands. Thermal poling insights were performed on these glassy and glass-ceramic materials and the experimental conditions had to be carefully optimized in the glass-ceramics to avoid electrical sparks and sample break associated with dielectric breakdown of the samples. Suitable and stable thermal poling treatments could be performed at 250 °C and 900 V under N2 atmosphere on both glass and glass-ceramics. These first insights pointed out a lower migration kinetic of sodium ions when compared to the precursor glass as well as a lower content of depleted ions, since part of sodium is supposed to be “frozen” inside the crystalline phase in glass-ceramics. Despite these lower kinetic poling conditions, a poled sodium depleted layer whose thickness depends on the poling time was successfully formed at the anode side. Reflectance infrared spectroscopy was also used to investigate the structural changes in the poled layer. These IR data pointed out that structural changes induced by thermal poling are mainly promoted in the phosphate network rather than tantalate units in both glass and glass-ceramics in agreement with a selective sodium migration from the remaining glassy phase. Macroscopic induced SHG measured by the Maker fringes technique is also consistent with the EFISH model and quantitative simulations of these data allowed to estimate second order nonlinear optical susceptibilities χ(2) ten to twenty times lower in the glass-ceramics than in the precursor glass. Such electric behavior is discussed in terms of dielectric properties of heterogeneous materials and interfacial polarization mechanisms between crystallites and glassy phase.< Leer menos