This work reports a triphenylphosphine-guided hyper-cross-linking self-assembly strategy to construct honeycomb-like bicontinuous P-doped porous polymers (HBPs) based on polylactide-b-polystyrene/4-diphenyl-phosphinostyrene (PLA-b-P(S/DPPS)) diblock copolymers. The triphenylphosphine (PPh3) groups derived from DPPS not only play as the cross-linkable monomer with S and DPPS but also serve as the strong P ligands for binding the metal species. Subsequently, Pd nanoparticles (NPs) can be effectly encapsulated into the synthesized HBPs by a simple impregnation reduction method. The resultant Pd@HBPs show more excellent catalytic performance for selective hydrogenations than the corresponding homogeneous catalysts and synthesized heterogeneous analogues. The great performance could be attributed to the advantage of the three-dimensionally (3D) honeycomb-like interconnected mesoporous structure, which allows the accessible catalytically active sites to be efficiently exposed toward reactants. This strategy represents a new method for the preparation of porous organic polymers with special morphologies and various functionalizations for potential applications including energy storage, adsorption, separation, and catalysis.