The redox chemistry of the homoleptic iron prismane cluster [{Cp*Fe}(3)(mu(3),eta(4:4:4)-As-6)] (A, Cp*=C5Me5) is investigated both electrochemically and synthetically. While its first oxidation leads to the diamagnetic species [{Cp*Fe}(3)(mu(3),eta(4:4:4)-As-6)][X] ([1][TEF], [1][FAl], [TEF](-)=[Al{OC(CF3)(3)}(4)](-), [FAl](-)=[FAl{O(1-C6F5)C6F10}(3)](-)), the second oxidation yields the paramagnetic [{Cp*Fe}(3)(mu(3),eta(4:4:4)-As-6)][TEF](2) ([2][TEF]2). The reduction of A leads to the monoanionic compound [K@[2.2.2]-cryptand][{Cp*Fe}(3)(mu(3),eta(4:4:4)-As-6)] ([K@crypt][3]), while a second reduction could only be traced spectroscopically. All compounds were comprehensively characterized, revealing the structural changes accompanying the described redox processes. All findings are supported by spectroscopic as well as computational studies.