The Xantphos-based HCP (X-HCP) was prepared, following an external knitting strategy (Scheme 1). In accordance with Yang et al., we employed AlCl3 as strong Lewis catalyst for the activation of the less reactive phosphine monomer. The successful crosslinking in the X-HCP skeleton was proven by Fourier-transform infrared spectroscopy (FTIR) (Fig. ), where the characteristic band at 2911 cm -1 shows the stretching vibration of the formed methylene bridges. The vanishing of the C-Cl vibration at 642 cm -1 indicates the substitution of chloride, whereas the broad band at 1611 cm -1 is assigned to the vibrations of the present aromatic units. The presence of Xantphos is clearly revealed by the preservation of the bands at 2952 cm -1 (-CH3), 1440 cm -1 (C-P) and X-ray fluorescence spectroscopy (XRF) confirms the presence of phosphorus, additional small residues of aluminum and chloride remained inside the network (Table ). In comparison to an ideal HCP with entirely crosslinked monomers, only one third of the monomeric Xantphos is incorporated in the final X-HCP. This difference is driven by the ability of the external crosslinker to interconnect with itself, without involving Xantphos. XRF confirms the uptake of ruthenium (0.31 wt%) in X-HCP-Ru after the ligand exchange (Scheme 1). The molar ratio between phosphorus and ruthenium of 27:1 indicates that the donor centers of the macroligand are either not all capable to coordinate or only partially accessible for the metal species. This imbalance may be caused by its topological conformation, which is characterized by a combination of HCP-typical amorphous as well as crystalline domains (Fig. ). Beside a non-ordered structure, the sharp reflexes of X-HCP in X-ray powder diffraction measurements coincide with those from the monomeric Xantphos. Thus, it seems that Xantphos units in the X-HCP framework arrange in a stacked manner, probably diminishing their ligating ability. The X-HCP exhibits a porosity with a specific surface area (BET) of 222 m 2 g -1 (Fig. ). Nitrogen physisorption reveals the presence of micropores and a broad distribution of mesopores. The distinct hysteresis, which is not closing, is known for non-rigid materials and is attributed to capillary condensation, pore blocking and swelling effects. Water vapor sorption measurements refer to the hydrophilic characteristics of the X-HCP. The gradual uptake relates to a moderate hydrophobicity, but proves a wettability, which is of importance for catalytic application in the aqueous phase (Fig. ). Thermogravimetric analysis (TGA) revealed a 7 wt% mass loss up to 350 °C, followed by a one-step decomposition at 450 °C (Fig. ). Furthermore, the morphology of the polydisperse particles were shown by scanning electron microscopy (SEM) (Fig. ) and indicate uniform particles with sizes between 200 and 500 µm. The absence of larger nanoparticle clusters was proven by transmission electron microscopy (TEM) (Fig. ).