Porphyrins have found application in a remarkable variety of areas such as sensors, ion selective electrodes, photodynamic therapy, and energy-transfer systems. Here, we demonstrate the extraction of 5,10,15,20-tetraphenylporphyrin (TPhP) and 5,10,15,20-tetra(4-pyridyl)porphyrin (TPyP) into a mixture of perfluorohexanes (FC-72) through noncovalent interactions with Krytox (1), a carboxylic acid terminated perfluoropolyether. We found that I transfers two protons to the TPhP tetrapyrrole ring to create the porphyrin dication (H2TPhP2+) in FC-72 while up to six protons are transferred to the TPyP pyridyl and tetrapyrrole nitrogens to create a hexavalent cation macrocycle in the fluorous phase. The total charge on TPyP is controlled by adjusting the concentration of 1 in the fluorous phase. In addition, we observed extraction of ZnTPyP from CDCl3 with 1/FC-72, while ZnTPhP is not extracted by 1/FC-72. We prepared the Zn salt of I and found that it extracts (from CDCl3) and metalates TPyP but not TPhP. Competitive binding between the porphyrins and an ethanol cosolvent hinders the extraction of both TPhP and TPyP and inhibits the formation of the TPyP hexacation in FC-72. By controlling the concentration of porphyrin, 1, and ethanol, it is possible to reversibly solubilize TPyP in the fluorous phase through noncovalent interactions between the pyridyl moieties and I while leaving the tetrapyrrole ring available to interact with metals or other substrates. In addition, both porphyrins and ZnTPyP are easily recovered from the fluorous phase using commercially available fluorous solid-phase extraction cartridges. Understanding noncovalent interactions in fluorous matrices should lead to development of more robust devices for sensing and energy transfer.