Ag(I) complexes synthesised by reacting AgO2C2F3 with 2-pyridinyl Schiff base ligands. Ag(I) atoms chelated by ligands in a bidentate mode via pyridinyl and imine N atoms. The anion coordinated either by monodentate or bridging two Ag(I) centres in a μ2-κ2O:O′ mode. The complexes have active sites for ring-opening polymerization of ε-caprolactone.