investigated the influence of different crosslinked phosphine units on the catalytic CO2 hydrogenation, following an organolithium synthesis route. to the monodentate PPh3 unit. However, the polymeric analog of dppe exhibited a loss of activity over consecutive recycling runs, which was attributed to structural alterations in the catalytically active metal complex. Subsequently, Gunasekar et al. applied a slightly modified catalytic system in a tubular reactor and demonstrated its stability in the continuous hydrogenation of CO2 to N-Ndimethylformamide. Ji et al. coupled PPh3-based ligating sites with surrounding N sites in order to enrich and activate CO2 in close proximity to the catalytically active Ru center. They prepared frameworks of varying topologies via aldimine condensation and obtained evidence for the beneficial synergy of Ru phosphine species and N species by comparing N-containing and Nabsent catalysts. Recently, Hu's group interconnected the prototypical PPh3 via an external knitting strategy and examined the catalytic activity of the Ru-or Ir-loaded hyper-crosslinked polymers (HCPs) in the CO2 hydrogenation to formate. Since the postsynthetic immobilization of the Ir precursor on the polyphosphine did not result in a metal uptake, they carried out direct crosslinking of the entire transition metal phosphine complex. In previous work, we studied this crosslinking approach and investigated systematically the influence of the crosslinking conditions of porous polyphosphines on their catalytic activity and stability in the CO2 hydrogenation to formate. Collectively, the previous works emphasize the crucial role of the macroligands for catalytically active metal centers in the CO2 hydrogenation to formic acid. Herein, we investigate the metal uptake of various precursors on the macroligands and compare catalysts, derived from the postsynthetic metalation of crosslinked polyphosphines or the direct knitting of entire metal phosphine complexes. In addition, the versatility of the incorporated phosphine building blocks enables the tailored variation of the ligating microenvironment, revealing its effect on catalytic performance. This systematic exploration of the catalytic system provides insight into the design strategy of stable and active solid catalysts for the hydrogenation of CO2 to formate.