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The reaction mechanism for the formation of the pseudo‐silaazatriene 1 (LN(SiMe3)2−Si−N−Si(L)NSiMe3; L=PhC−(NtBu)2) by the reaction of 1 equivalent of bis‐silylene (LSi−SiL; L=PhC(NtBu)2) with 3 equivalents of azide Me3SiN3 has been explored at M06/def2‐TZVPP//BP86‐D3(BJ)/def2‐TZVPP level of theory. The reaction mechanism is guided by the high Lewis basicity of the silicon lone pair and the high Lewis acidic character of Si−N bonds, as well as by the high tendency to eliminate N2 from Me3SiN3. The first step of the reaction is the formation of [3+1] cycloaddition product (I1) by the synergetic interactions of the lone pair on the silylene silicon with the π* molecular orbital of Me3SiN3 which is majorly localized on the terminal nitrogen atom, and the donation of the σ‐type lone pair on the nitrogen atom connected to the SiMe3 group with the Si−N σ* orbital on silylene. The elimination of N2 from I1 results in the formation of pseudo‐silaimine intermediate I2 having a dicoordinated, monovalent nitrogen atom. The most favourable pathway involves the second addition of Me3SiN3 followed by N2 elimination resulting bis‐silaimine intermediate I4‐P2. The highly reactive lone pair on the dicoordinated, monovalent nitrogen atom can be coordinated to the Si−N σ* MO of the second silylene moiety resulting in Si−N bond formation and Si−Si bond cleavage. This step is similar to the SN2′ reaction where the incoming nucleophile and the leaving group are on the same side resulting in the formation of silaimine I5. Further, the [3+1] cycloaddition of one more molecule of Me3SiN3 followed by N2 elimination results in the formation of silaimine intermediate I7. I7 undergoes 1,3‐silyl migration leading to the final product 1. The lone pairs on di‐ and tricoordinated nitrogen centres of all the intermediates are stabilized by hyperconjugative interactions. The delocalized hyperconjugative interaction stabilizes the lone pairs in 1. [ABSTRACT FROM AUTHOR]