Electrochromic characteristics of tris-bipicoline rhodium complex, [Rh (bipc.) ₃] Cl₃, are invetigated in DMF solution containing some electrolytes. This shows electrochromic characteristics with the color change from pale-yellow to red at reduction state in TBAP/DMF solution. At the presence of LiClO₄ in DMF solution, this complex shows neither electrochemical response nor electrochromic characteristics. From the results of DMF solution containing TBAP and LiClO₄ with several concentration ratio, electrochromic behavior of Rh (bipc.) ₃ complex is considerably affected by the interaction between Rh (bipc.) ₃ complex and cation species. Rh (bipc.) ₃ complex may interact with lithium cation, resulting in no electrochromic behavior. These interactions and/or the structure of the complex are also revealed to be affected by the electronic characteristics of the solvent.