The reaction between equimolar amounts of the isocyanide complexes [AuCl₃(CNR)] [R = 2,6-Me₂C₆H₃ (Xyl), 1a; 2,4,6-Me₃C₆H₂ (Mes), 1b; Cy, 1c; t-Bu, 1d] and tetrabutylammonium azide (2) proceeds in CH₂Cl₂ at room temperature for ∼10 min to furnish the gold(III) tetrazolates [n-Bu₄N][AuCl₃(CN₄R)] (3a-d), which were obtained in 89-95% yields after purification. Subsequent reaction between equimolar amounts of 3a-d and methyl trifluoromethanesulfonate (MeOTf) proceeds in CH₂Cl₂ at -70 °C for ∼30 min to give the corresponding gold(III) complexes [AuCl₃(C^aN(Me)N₂N^bR)]^a-b (5a-d) bearing 1,4-disubstituted tetrazol-5-ylidene ligands (69-75%). Complexes 3a-d were obtained as pale-yellow solids and characterized by elemental analyses (C, H, N), HRESI^--MS, FTIR, and ¹H and ¹³C{¹H} NMR spectroscopies. Complexes 5a-d were obtained as colorless solids and characterized by elemental analyses (C, H, N), HRESI⁺-MS, and 1D (¹H and ¹³C{¹H}) and 2D (¹H,¹³C-HMBC) NMR spectroscopies. In addition, the structures of 3a, 3b, 3c, and 5a were established by single-crystal X-ray diffraction. Analysis of the Wiberg bond indices (WI) for gas phase-optimized model structures of 3a-c and 5a computed using the natural bond orbital (NBO) partitioning scheme disclosed a higher degree of electron density delocalization in the CN₄ moiety of carbene 5a when compared to tetrazolate 3a-c. Results of DFT calculations for a model system reveal that the mechanism for the cycloaddition of an azide to the isocyanide ligand in [AuCl₃(CNMe)] is stepwise and involves nucleophilic attack of N₃ ^- on the N atom of CNMe followed by ring closure. The addition is both kinetically and thermodynamically favorable and occurs via the formation of an acyclic NNNCN intermediate, whereas the cyclization is the rate-determining step.