Designing new functional materials with increasingly complex compositions is of current interest in science and technology. Complex rare‐earth‐based chalcogenides have specific thermal, electrical, magnetic and optical properties. Tetragadolinium bis[tetraoxidosilicate(IV)] oxide telluride, Gd4(SiO4)2OTe, was obtained accidentally while studying the Gd2Te3–Cu2Te system. The crystal structure was determined by means of single‐crystal X‐ray diffraction. The compound crystallizes in the space group Pnma. Three symmetry‐independent gadolinium sites were determined. The excitation and emission spectra were collected at room temperature and at 10 K. Gd4(SiO4)2OTe appears to be a promising optical material when doped with rare‐earth ions.