Bis[bis(trimethylsilyl)methyl]gallium Bromide and Monomeric {Bis[bis(trimethylsilyl]methyl]gallium} [Tris(trimethylsilyl)silyl]telluride [(Me3Si)2CH]2Ga–TeSi(SiMe3)3Bis[bis(trimethylsilyl)methyl]gallium bromide GaBr[CH(SiMe3)2]2 (4), prepared from Ga2Br4 · 2 dioxane and bis(trimethylsilyl)‐methyllithium in the molar ratio of 1:3, reacts with the sterically high‐shielded lithium tris(trimethylsilyl)silyltelluride · DME to yield [(Me3Si)2CH]2Ga–TeSi(SiMe3)3 (5). 5 can also be synthesized by a metathetic reaction between tetrakis‐[bis(trimethylsilyl)methyl]digallium(4) and bis[tris(trimethylsilyl)silyl]ditellane in toluene at 100°C. A crystal structure determination shows the compound to be monomeric in the solid state and the atoms of the central C2Ga–TeSi moiety to lie in the mirror plane of the molecule. The short Ga–Te distance of 253.5(1) pm as well as a hindered rotation (ΔErot ≈︁ 50 kJ · mol‐1) as detected by NMR measurements might be interpreted in terms of a π interaction between gallium and tellurium.