Liquid metal salts are electrolytes with the highest possible metal concentration for electrodeposition, because the metal ion is an integral part of the solvent. This paper introduces the new ionic silver complexes [Ag(MeCN)₄]₂[Ag(Tf₂N)₃], [Ag(MeCN)][Tf₂N] and [Ag(EtIm)₂][Tf₂N], where MeCN stands for acetonitrile, EtIm for 1-ethylimidazole and Tf₂N is bis(trifluoromethylsulfonyl)imide. These complexes have been characterized by differential scanning calorimetry, single crystal X-ray crystallography, thermogravimetrical analysis, Raman spectroscopy and cyclic voltammetry. [Ag(MeCN)₄]₂[Ag(Tf₂N)₃] is a room temperature ionic liquid. Smooth silver layers of good quality could be deposited from it, at current densities of up to 25 A dm⁻² in unstirred solutions. [Ag(EtIm)₂][Tf₂N] melts at 65 °C and can be used as an electrolyte for silver deposition above this temperature. [Ag(MeCN)][Tf₂N] has a melting point that is too high to be useful in electrodeposition. Addition of thiourea or 1H-benzotriazole to the electrolyte decreased the surface roughness of the silver coatings. The morphology of the metal layers was investigated by atomic force microscopy (AFM). Adsorption of 1H-benzotriazole on the silver metal surface has been proven by Raman spectroscopy. This work shows the usefulness of additives in improving the quality of metal films electrodeposited from ionic liquids.