The efficiency for partitioning small organic compounds from fluorinated solvents of varying quality into highly cross-linked, macroporous, and insoluble organic polymers is described. The solvating qualities of the poly(acrylates) together with the solvating quality of the solvent are key to describing the partitioning thermodynamics. Partitioning measurements for 9-anthracene methanol 1 are reported as a function of fluorous content in perfluoromethylcyclohexane (PFMC):hexanes mixtures, comonomer structure and loading, and temperature. The best comonomer for the sorption of 1 is methacrylamide. Concentration enhancements of up to similar to200-fold are obtainable, and are proposed to account for previously observed rate accelerations in catalyst-containing porous polymers. Partition efficiency (PE) measurements, described as the ratio of polymer to original solution concentrations, are presented for a variety of organic compounds. The PE is sensitive to analyte structure and ranges from 1 to 170 (180 being the maximum under the conditions employed), with linear alkanes at the low end of the spectrum and polar functional groups at the opposite.