The radical cation and dication salts of a tetrathiafulvalene (TTF) derivative functionalized with two amino groups have been successfully stabilized and isolated specifically by chemical oxidation using a polyfluoroalkoxyaluminate weak coordinating anion, [Al(OR_F)₄]⁻ (OR_F = OC(CF₃)₃). These compounds were characterized by UV-Vis-NIR absorption spectroscopy, ¹H NMR, EPR, and X-ray single crystal diffraction, respectively. Comprehensive research on their structure–property relationship in conjunction with theoretical calculations has been carried out.