Because of the importance of the CpRe(CO)₃/Cp*Re(CO)₃ system, it is promising to investigate complexes having Re(CO)₃ group coordinated to cyclopentadienyl mimics which possess different steric and electronic properties. This is among the several means to build a family of Re(II) electron transfer mediators. Since the hydridotris(pyrazolyl)borate (Tp) and hydridotris(3,5-dimethylpyrazolyl)borate (Tp*) ligands have been long used as analogues of Cp and Cp* ligands respectively due to their abilities to serve as facially coordinating, anionic six-electron donors, research was begun with Tp/Tp* ligand system. In this preliminary work, the anodic electrochemistry of Tp*Re(CO)₃ was studied in CH₂Cl₂ containing [NBu₄][B(C₆F₅)₄] as supporting electrolyte. Cyclic voltammetry experiments show a reversible 1-electron transfer process between Tp*Re(CO)₃ and its 17-electron radical cation. The spectral characterization of the highly stable radical cation will be discussed, as well as its possible electron transfer reactions with olefins.