The formation of new lead-free materials based on alkali/bismuth couple was studied in the ternary system A2O-Bi2O3-TiO2 (A=Li, Rb). The phase identification has been performed by X-ray diffraction. In both case, compounds with perovskite structure were not observed. However, with the lithium-ion, we can notice the formation of a pyrochlore-like compound, isostructural with Bi2Ti2O7. This compound is known as metastable and decomposing at 650°C. Interestingly, in our case it has been stabilized until 1100°C by the addition of lithium.