Spontaneous ion separation of the scorpionate beryllium complex, TpBeI 1 (Tp = 1-trispyrazolylborate), occurs upon treatment with THF, yielding [TpBe(thf)]I 2, which was characterized by heteronuclear NMR spectroscopy (1H, 9Be, 13C) and structurally characterized by single crystal X-ray diffraction. 2 represents a rare example of a structurally characterized monocationic beryllium complex, and to the best of our knowledge, the synthesis of 2 by a solvent-induced ion separation has previously only been observed in the reactions of beryllium dihalides with strong Lewis bases.