The one-electron oxidation and protonation of diferrocenylphenylphosphine (Fc2PhP) leads to the formation of two distinct, stable cationic phosphorus species, namely the radical cation [Fc2PhP][B(C6F5)4] and the phosphonium ion [Fc2PhPH][B(C6F5)4]. Although their solid-state structures are remarkably similar, the bathochromic shift in the UV-Vis absorption spectrum of the radical cation, signals with distinct multiplicities in the31P NMR spectra, as well as contrasting quadrupole splitting values in the57Fe Mößbauer spectra, elucidated the differences between the two cations.