This article reports the reduction of the chloride [PhC(NtBu)2]GeCl with potassium in THF to afford the reddish crystals of [PhC(NtBu)2]2Ge2 (2). The molecule of 2 contains a Ge−Ge bond. The X-ray structure and DFT calculation indicate that the Ge−Ge bond possesses an unusual gauche-bent geometry. The Ge−Ge bond length in 2 is 2.570 Å, which is very close to the single Ge−Ge interaction (2.61 Å) but significantly longer than that for typical digermenes, R2GeGeR2 (2.21−2.51 Å) and the two structurally characterized digermynes (2.2850 Å and 2.2060 Å), which proves that there is no multiple bond character in 2.