Ba20Hg103, the next Hg-rich binary barium mercuride after BaHg11 and BaHg6, was synthesized from melts of the elements, which were slowly cooled from 550 to 200 ◦C. It forms a new complex cubic structure type (F4̄3m, a = 2333.30(10) pm, Z = 4, R1 = 0.0651) with four Ba und 13 Hg positions as determined by means of single-crystal X-ray diffraction. The structure can be best described by decomposi...