Consequently, the phosphine units are interconnected in the presence of AlCl3 via Friedel-Crafts alkylation or Scholl coupling, depending on the choice of solvent. Owing to the insufficient rigidity of the sole phosphine units in the non-porous frameworks, the shift towards aromatic crosslinker units introduces porous structures, originating from the self-crosslinking capabilities of the benzylic and biphenylic linkers. This structural crafting affects the ruthenium uptake of the phosphine ligands, relating to an improved accessibility to the coordination sites. The ruthenium immobilized macroligands exhibit excellent catalytic performances in the hydrogenation of CO2 to formic acid, accompanied by a continuous degradation of the active species during a certain induction phase. Detailed investigations reveal the structural alteration of the porous structure in the AlCl3-derived polyphosphine, which are less pronounced for frameworks crosslinked in the presence of FeCl3 or triflic acid. The collapse of the porous macroligands under catalytic conditions is prevented by adjusting high crosslinking densities in the polyphosphine synthesis.