A series of coinage metal complexes bearing rarely explored ortho-silylated phosphine is reported. The treatment of diphenyl(2-(trimethylsilyl)phenyl)phosphine (1) with CuCl and [Cu(CH₃CN)₄]BF₄ furnished the corresponding neutral [(1)CuCl]₂ (2) and mono-cationic [(1)₂Cu(CH₃CN)]BF₄ (3) complexes, respectively. The reactions of 1 with AgX (X = BF₄⁻, NO₃⁻) in 2 : 1 ratio furnished the corresponding mono cationic dicoordinate silver(I) complexes of the type [(1)₂Ag]X (X = BF₄⁻ (4a), NO₃⁻ (4b)). The ortho-silylated phosphine ligand (1) was conveniently converted into the corresponding sulfide (5a) and selenide (5b) species, and their reactions with [Cu(CH₃CN)₄]BF₄ yielded mono-cationic, homoleptic tris(silylphosphinochalcogenide)copper(I) complexes of the type [(5a/5b)₃Cu]BF₄ (6a/6b). The molecular structures of 2–4 and 6 were established by single-crystal X-ray diffraction analysis. The copper complexes 2, 3, and 6a were employed as catalysts in azide–alkyne cycloaddition reactions. Among these complexes, 3 was extensively used in the preparation of various mono- and bis-triazoles consisting of tolyl, benzyl, carbazolyl, and propargylic ether groups. Three sets of substituted triazole derivatives were achieved under mild conditions by employing copper(I) catalytic systems. The mechanistic studies indicated the formation of a heteroleptic copper(I) triazolide intermediate which was detected by high-resolution mass spectral analysis.