A convenient method for the synthesis of silver alkynyl compounds containing different nuclearities has been developed. The reaction of AgC[triple bond, length as m-dash]CBu(t) and AgX (X = CF3CO2(-), C2F5CO2(-)) in the presence of auxiliary ligands L (L = bipyridine, bipy; 1,10-phenanthroline, phen; 2-(diphenylphosphino)pyridine, dppy) under different conditions afforded a family of new silver alkynyl compounds, namely, [Ag3(bipy)(C[triple bond, length as m-dash]CBu(t))(CF3CO2)2]n (), [Ag4(bipy)2(C[triple bond, length as m-dash]CBu(t))(CF3CO2)3]n (), [Ag6(phen)3(C[triple bond, length as m-dash]CBu(t))2(C2F5CO2)4(MeOH)(EtOH)] (), [Ag8L4(C[triple bond, length as m-dash]CBu(t))2(C2F5CO2)6] (L = bipy, ; L = phen, ), [Ag10(dppy)2(C[triple bond, length as m-dash]CBu(t))6X4] (X = CF3CO2(-), ; X = C2F5CO2(-), ), [Ag12(bipy)2(C[triple bond, length as m-dash]CBu(t))8(C2F5CO2)4] () and [Ag12(phen)4(C[triple bond, length as m-dash]CBu(t))6(CF3CO2)6]·2EtOH (). Single-crystal X-ray analysis revealed that compounds and display infinite-chain structures, while the other seven compounds are discrete molecules containing silver nuclearities varying from 6 to 12. The formation of various structural motifs depends on the reactant ratios and the ligands/anions with different nature.