Thermally-robust bismuthanylstibanes are prepared in a one-step, high yield reaction, providing the first examples of neutral Bi–Sb σ-bonds in the solid state. DFT calculations indicate that the bis(silylamino)naphthalene scaffold is well-suited for supporting otherwise labile bonds. The reaction chemistry of the Bi–Sb bond is debuted by showing fission using NH₃BH₃ and insertion of a sulfur atom, the latter providing the first example of a Bi–S–Sb motif.