The reactions of [Pt-3n(CO)(6n)](2-) (n = 2-4) homoleptic Chini-type clusters with stoichiometric amounts of Ph2PCH2CH2PPh2 (dppe) result in the heteroleptic Chinitype clusters [Pt-6(CO)(10)(dppe)](2-), [Pt-9(CO)(16)(dppe)(2-), and [Pt-12(CO)(20)(dppe)(2)](2-). Their formation is accompanied by slight amounts of neutral species such as Pt-4(CO)(4)(dppe)(2) Pt-6(CO)(6)(dppe)(3), and Pt(dppe)(2). A similar behavior was observed with the chiral ligand R-Ph2PCH(Me)CH2PPh2 (R-dppp), and two isomers of [Pt-9(CO)(16)(R-dppp)](2-) were identified. All the new species were spectroscopically characterized by means of IR and P-31 NMR, and their structures were determined by single-crystal X-ray diffraction. The results obtained are compared to those previously reported for monodentate phosphines, that is, PPh3, as well as more rigid bidentate ligands, that is, CH2=C(PPh2)(2) ((PP)-P-boolean AND), CH2(PPh2)(2) (dppm), and o-C6H4(PPh2)(2) (dppb). From a structural point of view, functionalization of anionic platinum Chini clusters preserves their triangular Pt-3 units, whereas the overall trigonal prismatic structures present in the homoleptic clusters are readily deformed and transformed upon functionalization. Such transformations may be just local deformations, as found in [Pt-9(CO)(16)(dppe)](2-), [Pt-9(CO)(16)(R-dppp)(2-), [Pt-12(CO)(22)(PPh3)(2)](2-), and [Pt-9(CO)(16)(PPh3)(2)](2-); an inversion of the cage from trigonal prismatic to octahedral, as observed in [Pt-6(CO)(10)(dppe)(2-) and [Pt-6(CO)(10)(PPh3)(2)](2-); the reciprocal rotation of two trigonal prismatic units with the loss of a Pt-Pt contact as found in [Pt-12(CO)(20)(dppe)(2)](2-) .