New opportunities for photonic components result from the discovering of the second harmonic generation (SHG) in thermally poled glasses in the earliest 1990s. It has attracted a lot of interest because it offers new developments in the optical glassy material research. In this context a new tellurite glass with 70%TeO2–25%Pb(PO3)2–5%Sb2O3 composition has been developed and characterized. The structure of the unpoled glass has been studied by IR, Raman, and XAFS spectroscopy. Optical properties of transmission like the linear refractive index and third-order non-linear optical susceptibility χ(3) as well as dielectric susceptibilities have also been investigated. A second harmonic signal was observed for the poled glass which is an order of magnitude better than the silica glass efficiency.