Diphenyl‐o‐silaborane (1) can be obtained by sublimation as colourless crystalline material in a yield of 23%. The disilaborane 1 was characterized by NMR spectroscopy, mass spectrometry and X‐ray structure analysis. The neutral closo cluster 1 reacts with [Zr(NMe2)4] or [Ta(NMe2)5] to give the dimethylamide adduct [(Me2N)(PhSi)2B10H10]– of the disilaborane.