Water-soluble arene ruthenium complexes have been intensively studied as cytotoxic compounds for the last fifteen years, notably owing to the promising in vitro and in vivo evaluations of, respectively, RAPTA-C (eta(6)-p-MeC6H4Pri)Ru(P-pta)Cl-2 (pta = 1,3,5-triaza-7-phospha-tricyclo-[3.3.1.1]decane) from Dyson's laboratory, and the (i-arene)Ru(en)Cl](+) (en = ethylenediamine, RAED) family of compounds from Sadler's laboratory. In this account we describe the discovery of thiolato-bridged dinuclear arene ruthenium complexes and highlight subsequent developments in the field, including their syntheses, structures, and the recent strategies for the design of thiolato-bridged dinuclear arene ruthenium bioconjugates. (C) 2015 Elsevier B.V. All rights reserved.