Three 1D multinuclear silver(I) alkynyl compounds, [Ag11(CCtBu)6(CF3COO)5(CH3OH)]n (1), [Ag11(CCtBu)7(CH3COO)4]n (2) and [Ag12(CCtBu)7(CF3COO)5·H2O]n (3), constructed from AgCCtBu ligand and CF3COO−/CH3COO− auxiliary ligand, have been obtained by changing the type and source of the auxiliary ligand as well as adjusting the pH value in different solvents. The synthesis of 1–3 indicates that this kind of 1D multinuclear Agn (n = 11, 11, 12) alkynyl chain can be isolated through a facile one-pot process. Among these, an infinitely extended 2D supramolecular network is fabricated from 1D chains of 1 via hydrogen bonds, while 3 crystallizes in the chiral space group P21. In addition, the solid state optical diffuse reflection spectra and luminescence spectra of 1–3 have been obtained. Compound 2 is taken as an example to study the electrochemical behaviour of this kind of compound, and the results indicate that 2-CPE possesses good electrocatalytic activity toward the reduction of nitrite.