[Ag(NH3)2]+ ions are chosen as an initial reaction precursor because of its simple displacement reaction and intrinsic arrangement as well as specific coordination directionality. Two new silver(I) ammine complexes, Ag2(NH3)HL2 (2) and Ag2(NH3)2HL3 (3), were obtained by a simple substitution reaction between [Ag(NH3)2]+ ions and pyridine‐4,5‐imidazoledicarboxylic acid [H3L2 = 2‐(3′‐pyridyl) 4,5‐imidazoledicarboxylic acid and H3L3 = 2‐(4′‐pyridyl) 4,5‐imidazoledicarboxylic acid]. Silver dimers are connected into a 2D layer and 1D chain in complexes 2 and 3, respectively. In complex 2 two kinds of displacement reactions (mono‐substituting and bis‐substituting) occurred between the ammine molecules in [Ag(NH3)2]+ ions and H3L2, however, only the mono‐substituting reaction occurs in complex 3.