A family of silver(i) complexes, [Ag2(L)2(OOCCF3)2] (), [Ag(L)0.5(OOCCF3)] (), [Ag(L)2](OOCCF3)(H2O)2 (), was obtained by reactions of 4,4'-di(2-oxazolinyl)biphenyl (L) and AgOOCCF3 in different reaction media. Compound has a 1D chain structure with alternative connections between the Ag(i) and L ligand. When the crystal nucleation inductor, pyrazine, was added into the reaction system, complex was isolated with no pyrazine observed in its structure. In , the 1D inorganic chains formed by Ag(i) cations and OOCCF3(-) anions were connected by the L ligand to produce a 2D network. When a different inductor, imidazole, was added into the reaction system, with (4,4) topology was synthesized, and again no imidazole was found in . When were used as catalysts for cycloaddition reactions between imino esters and methyl acrylate, affords the highest yield, in which the particular size of the channels in led to its selective catalytic performance.