A library of cross-linked poly-porphyrins with porous and network structures were prepared via the Sonogashira polymerization method to address the issues of the porphyrin monomers in separation, recycling and purification during the photocatalytic process. Two types of porphyrin monomers (dibromodiacetylenic porphyrin and tetrabromoporphyrin) were designed and the porphyrin-based porous organic polymer (PPOP-1) was obtained through self-polymerization of dibromodiacetylenic porphyrin and three poyporphyrins were obtained through the copolymerization of tetrabromoporphyrin and various linkers containing dialkynes (1, 7-octadiyne, p-phenylenediyne, and biphenyl). The surface morphology and pore structure of the polymers are characterized by scanning electron microscopy and physical adsorption. All four polymers had uniform ellipsoid morphology and microporous structures. PPOPs were used as metal-free heterogeneous photocatalysts and the photocatalytic activity for C-N and C-S bonds were confirmed through the visible light-induced oxidation of dibenzylamine, bisaminothioketal and dibenzyl sulfide. The PPOPs maintained excellent catalytic activity after five cycles.