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Utilization of CO₂ for the production of fine chemicals has become a research hotspot for a long time. In order to make use of CO₂, we developed a highly efficient heterogeneous catalyst (denoted as Pd@POPs) for the N-formylation reaction of amine and CO₂ under mild conditions. The Pd catalyst was based on a porous organic polymer derived from the solvothermal polymerization of vinyl-functionalized PPh₃. A series of characterizations and comparative experiments demonstrated that the Pd@POPs catalyst has high BET (Brunauer-Emmett-Teller) surface areas, hierarchical pore structure, and uniform dispersion of Pd active sites resulting from the formation of strong coordination bonds between Pd species and P atoms in the porous organic polymer (POP) support. In addition to the excellent activity, the Pd@POPs catalyst shows good stability for the N-formylation reaction of amine and CO₂.