Since the screening of various phosphine ligands revealed the successful properties of bidentate diphosphines for the formation of active homogeneous catalysts, we extended the range of incorporated phosphine building blocks and crosslinked bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), xantphos and BINAP (Scheme 1). All the resulting polyphosphines exhibit C-P vibrations (1434 cm -1 ) in the FTIR spectra, indicating the presence of phosphine moieties in the insoluble framework (Fig. ). They coincide in the aromatic skeleton vibrations (1481 cm -1 and 1584 cm -1 ) and show distinct deformation vibrations of the aromatic C-H bonds (660 cm -1 -760 cm -1 ). Aliphatic C-H vibrations (2820 cm -1 -2980 cm -1 ) suggest crosslinking of the aromatic building units via alkyl bridges, while these are less pronounced for P-BINAP. In general, the frameworks P-dppm, Pdppe and P-dppp, derived from the structurally close Ph2P(CH2)nPPh2 diphosphines, exhibit comparable vibrational patterns. P-Xantphos preserves the structural elements of the monomeric phosphine (Fig. ), referring to the peaks at 2952 cm -1 (-CH3) and 1233 cm -1 (C-O-C), whereas for P-BINAP the characteristic aromatic deformation vibrational bands (631 cm -1 -822 cm -1 ) of the monomer are retained (Fig. ). The structural elements of the Xantphos and BINAP monomers also appear in the topological conformation of the respective macroligands analyzed by X-ray powder diffraction (XRD) (Fig. ). P-Xantphos and P-BINAP both have HCP-typical amorphous as well as crystalline domains, whose sharp reflexes coincide with those of the monomer (Fig. ). Thus, it seems that the phosphine units are partially arranged in a stacked manner in the slightly flexible polyphosphines, similar to the order of the monomer crystallinity. P-PPh3, P-dppm, P-dppe and P-dppp are XRD-amorphous, but exhibit two very broad reflexes at 2θ values of 10 ° and 21 °, suggesting no significant long-range ordered domains. XRF measurements confirm the presence of phosphines in the framework, although only a fraction of the initial amount of phosphine (one-third to one-half) is present in the polyphosphines formed (Table ). As described above, their incomplete incorporation can be associated to the internal crosslinking of the aromatic crosslinker, without involving the phosphine building block.