To investigate the effect of X in ambiphilic compounds BiX(o-PPh2-C6H4)(2), PBiP-X, on metallophilic Pt-Bi interactions in its PtCl2 complexes two new derivatives PBiP-Me and PBiP-C6F5 were synthesized. Reaction with dichloro(1,5-cyclooctadiene)platinum(II) led to the platinum-(II) complexes [PtCl2(PBiP-Me)], 3, and [PtCl2(PBiP-C6F5)], 4, which together with the halide [PtCl2(PBiP-Cl)], 2, reported previously, establish a series of related PBiP-X complexes differing accessing [PtCl2(PBiP-OTO], 5, through the reaction of 2 with AgOTf. Analysis of the geometrical and electronic structures of these complexes revealed that in all cases the platinum(II) centers act as donors (through their filled d(z)(2) orbitals) to the bismuth(III) centers (possessing sigma*(Bi-X)/6p acceptor orbitals). The strength of these interactions increases with increasing electron-withdrawing character of X, which supports the conceptual approach in constructing this new class of compounds.