Silver is proving to have a number of medicinal applications; as an antiseptic, an antibacterial, and an anti-inflammatory, while any biological role for it is currently unknown. Silver compounds and their therapeutic potentials are under consideration from many research groups, while a number of early reviews recording the advances of silver(I) chemistry are also available. However there is no recent report on the screening for the antitumor potential of silver(I) compounds. This review focuses upon results obtained on the anti-proliferative activity of silver compounds in the past years. This survey shows that silver(I) complexes containing various type of ligands such as carboxylic acids, amino acids, nitrogen, phosphorus or sulfur donor ligands, exhibit selectivity against a variety of cancer cells. The role of the coordination number, which is related to either the stability or hydrophilicity–lipophilicity of a complex, is not clearly elucidated within this review.