The one-electron oxidation of the diiron complex [Fe2(CO)4(κ2-dppe)(μ-pdt)] (1) (dppe = Ph2PCH2CH2PPh2; pdt = S(CH2)3S) has been investigated in the absence and in the presence of P(OMe)3, by both electrochemical and theoretical methods, to shed light on the mechanism and the location of the oxidatively induced structure change. While cyclic voltammetric experiments did not allow to discriminate between a two-step (EC) and a concerted, quasi-reversible (QR) process, density functional theory (DFT) calculations favor the first option. When P(OMe)3 is present, the one-electron oxidation produces singly and doubly substituted cations, [Fe2(CO)4–n{P(OMe)3}n(κ2-dppe)(μ-pdt)]+ (n = 1: 2+; n = 2: 3+) following mechanisms that were investigated in detail by DFT. Although the most stable isomer of 1+ and 2+ (and 3+) show a rotated Fe(dppe) center, binding of P(OMe)3 occurs at the neighboring iron center of both 1+ and 2+. The neutral compound 3 was obtained by controlled-potential reduction of the corresponding cation, while 2 was quantitatively produced by reaction of 3 with CO. The CO dependent conversion of 3 into 2 as well as the 2+ ↔ 3+ interconversion were examined by DFT.