Reactivity of sterically demanding lithium (fluorosilyl)silylphosphanides with GeI yields green, cubic crystals in moderate yield. The identity of this species was investigated using only multinuclear NMR, elemental analysis, and UV-vis. Computational calculations (at the CIS level with the ab initio Los Alamos pseudopotential method (LAN L 1 DZ)) of the diphosphagermylene electronic structure was in agreement experimentally-derived electronic transition values. Due to disorder, the crystal structure of the diphosphagermylene could not be investigated.