Second harmonic generation (SHG) in poled glasses opens new opportunities in material research and device development for optics. Within this context (1−x)LaMgB5O10–xTiO2 and glasses have been formed and characterized. The structure of unpoled glasses has been studied by IR, Raman, and XAFS spectroscopies. Optical properties of transmission like linear refractive indexes and third-order non-linear optical susceptibility χ(3) have been investigated. A second harmonic signal was observed for each thermally poled composition, except for the LaMgB5O10 matrix glass.