The amorphous La4Ti9O24 microspheres were fabricated by a containerless flame-spraying method. The morphologies, structures, components and thermal stabilities of the microspheres were investigated by scanning electron microscope, optical microscope, X-ray powder diffraction apparatus, energy dispersive x-ray diffraction analysis and differential scanning calorimetry measurement. The as-prepared microspheres were transparent, and possess high reflective index. We further studied the optical application of these glass microspheres with high-reflective-index. The coating of La4Ti9O24 glass microspheres greatly increased the reflection of glass slide as substrate in the wide wavelength range (300-2000 nm), which is very useful for some special surfaces that require illumination from reflection of light rays, such as protective reflective helmet or clothes, road side signs, etc. In addition, it can be used as heat reflective layer, which solves the urban heat island effect.