A series of silver carboxylates containing unsaturated groups within the ligand have been synthesised [AgO2CR, R = CH2CN (1), H2CCH (3), H2CCHCH2CH2 (5), Me(H)CC(Me) (8), Ph(H)CCH (11)], along with their triphenylphosphine [AgO2CR(PPh3)2, R = CH2CN (2), H2CCH (4), H2CCHCH2CH2 (6), Me(H)CC(Me) (9), Ph(H)CCH (12)] and 1,2-bis(phenylthio)ethane adducts [AgO2CR(PhSCH2CH2SPh)2, R = H2CCHCH2CH2 (7), Me(H)CC(Me) (10)]. The structures of 2, 6, 8 and 9 have been determined by single crystal X-ray diffraction; the adducts are all four-coordinate at silver with a chelating carboxylate, while 8 adopts a polymeric structure based on dimeric units and in which an approximately octahedral geometry at silver is attained by additional weak intermolecular Ag⋯O and π-Ag⋯CC interactions. Silver films have been grown by aerosol-assisted chemical vapour deposition using 6, 7, 9 and 10; no film was obtained with 2, while only a very thin film was generated by 12. Films grown from the sulfur-containing adducts 7 and 10 were rough and poorly reflective, while films from 6 and 9 were of superior quality, being smooth and highly reflective.