The synthesis of the alkoxide [OC(tBu)(CF3)2]− by the reaction of tBuM-reagents (M = Li; MgX) with hexafluoroacetone was attempted. This alkoxide was anticipated to be a good building block for novel weakly coordinating anions. However, in all attempted syntheses - also supported by theoretical DFT calculations - it was shown that [H]− addition is favored over [tBu]− addition. Thus compounds like [(Li(OC(H)(CF3)2]4·2Et2O (1) and (CF3)2(H)COMgCl·(OEt2)2 (4) were formed. An unexpected result was the formation of (THF)3LiO(CF3)2OC(H)(CF3)2(2), an addition compound built from [(CF3)2C(H)O]− and hexafluoroacetone. The alkoxy-alkoxide 2 could be useful for further applications.