Two new cobalt-bis(dithiolene)-IMes (IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) complexes have been isolated, and a systematic solid-state structural characterization using single crystal X-ray diffraction studies was undertaken to confirm the identity of the complexes. (IMes)Co(S2C2Ph2)2 (1) crystallizes in a monoclinic space group I2/a, while (IMes)Co(S2C2(C6H4-p-OCH3)2)2 (2) crystallizes in a triclinic space group P1¯. A detailed solid-state structural analysis of 1 and 2 revealed that the extended structure is stabilized by a series of CH…S interactions. As validated using electrochemical studies, the binding of IMes to the cobalt atom may be electrochemically controlled by applying a suitable redox potential. These studies indicate that compounds 1 and 2 are expected to act as an effective electrochemical host, enabling them to be used as precursors to release IMes under environmentally benign conditions.