The BaTi2O5 (BTO) and 35La2O3-65Nb2O5 (LNO) amorphous microspheres without conventional network-forming oxides were fabricated by a containerless flame-spraying technique. The results showed that transparent BTO and LNO glass microspheres were successfully prepared. All the BTO glass microspheres have smooth surfaces and no crystalline traces, indicating they are amorphous glass with diameters ranging from 8 to 40 μm. Most of the LNO glass microspheres have diameters of 10 to 40 μm, which are amorphous glass with smooth surfaces. And a small number of LNO microspheres have large particle diameters, which possessing micron-sized grains on their surfaces. The BTO and LNO glass microspheres have high refractive index of 2.20 and 2.23, respectively, which are very promising to be applied as window, lens and reflection film materials.