Lead-free Cs4SnBr6 nanostructures were synthesized using the high-temperature wet chemical method with as prepared cesium oleate and oleylammonium bromide. A new type of the SiO2 layer formation method was followed using TEOS and m-cresol. Phase stability of the Cs4SnBr6 and Cs4SnBr6/SiO2 aged samples was analyzed by the X-ray diffraction method. Transmission electron microscopy micrographs show that the hexagonally shaped particles covered with a thin SiO2 layer for Cs4SnBr6/SiO2 and were verified with TEM-EDS spectra. Synthesized particles showed a bright orange colour fluorescence emission under UV light and were confirmed with fluorescence emission spectroscopy.