The substitution reactions of H2GeLiF (G) with SiH3X (X = F, Cl, Br) were investigated using calculations performed at the QCISD/6-311++G (d, p)//B3LYP/6-311+G (d, p) level of theory. The results led to the following conclusions. (i) The substitutions are nucleophilic reactions. There are two substitution paths, I and II, which both lead to the germane H2GeFSiH3. The enantiomers of this germane are obtained via these two paths if an H in SiH3X is replaced with a different group or atom. (ii) Both substitution pathways show the same order of barrier heights (SiH3F > SiH3Cl > SiH3Br). The difference between the bond energies of Li–X and Si–X may explain the precedence among the substitution reactions of G with SiH3X. Path I has a lower activation barrier than path II, indicating that path I is more favorable. (iii) Comparison between the relevant insertion and substitution reactions shows that substitutions are more favorable and that the substitution product H2GeFSiH3 predominates over the insertion product. (iv) The substitution reactions of H2GeLiF with SiH3X are exothermic.