To explore the influence of various anions on the self‐assembly and properties of silver complexes, reactions of anions of silver salts with 2,2′‐(1,4‐butanediyl)bis‐1,3‐benzoxazole (BBO) afforded four complexes, formulated as [Ag2(BBO)2(p‐toluenesulfonate)2] (1), {[Ag(BBO)(picrate)]}∞ (2), {[Ag(BBO)1/2(o‐coumarate)]·DMF}∞ (3) and {[Ag2(BBO)3](PF6)2}∞ (4). These complexes were characterized using elemental analysis, infrared spectroscopy and single‐crystal X‐ray diffraction. The crystal analysis results show that under the influence of coordination modes and steric hindrance of anions, the complexes exhibited binuclear (1), one‐dimensional polymeric (2 and 3) and two‐dimensional polymeric (4) structures. Compared with the BBO ligand, only complex 1 has a new emission peak at 428 nm, which is attributed to ligand–metal charge transfer. The emission peaks of complexes 2–4 are similar to those of the BBO ligand, which can be due to π–π* and n–π* transitions. These results indicate that anions can modulate the structures and luminescent properties of silver complexes. Moreover, cyclic voltammograms of 1–4 indicated an irreversible Ag+/Ag couple with the order of reversibility being 2 > 1 > 4 > 3. In vitro antioxidant experiments showed that complex 3 has significant antioxidant activity against superoxide and hydroxyl radicals.