In spite of the general oxophilic character and λ5 valence state accessibility of phosphorus centers, the oxidation of phosphanes bearing proximal positive charges remains challenging, in particular for dicationic representatives. Previously described diimidazolo- and diimidazolio-phosphane substrates were first resumed in the P-phenylated series, where the reported absence of coordinating ability of the N,N-dimethylated dication towards a neutral Rh(I) center is here confirmed towards a promoted oxygen atom. By contrast, the P-tert-butylated homologue is shown to undergo P-oxidation to give a stable gem-dicationic phosphine oxide (in 91% yield with m-CPBA). The latter could also be obtained by N,N-dimethylation of the neutral diimidazolo-phosphine oxide precursor. The strict covalent vs. dative character of the N2C–P bond in dicationic systems (N2C+)2P(X)R (R = Ph, tBu; X = lone pair, :O) has been investigated by DFT calculations on a model series where (N2C+) = 1,3-dimethyl-1H-imidazolio-2-yl. The relative magnitude of Gibbs free energies of the homolytic and heterolytic dissociation modes shows that diamidinio-phosphines and corresponding P-oxides are not N2C → P donor–acceptor adducts (as mono(amidinio)phosphines are), but rather true gem-dicationic phosphines and phosphine oxides in the strict sense, respectively.