A novel construction strategy of monolithic capillary column for selectively enriching perfluorinated persistent organic pollutants was proposed. The organic–inorganic hybrid fluorous monolithic capillary column was synthesized by a “one-pot” approach via the polycondensation of γ-methacryloxypropyltrimethoxy-silane, then in situ copolymerization of 1H,1H,7H-dodecafluoroheptyl methacrylate and vinyl group on the precondensed siloxanes. The obtained monolithic columns were systematically characterized. The results demonstrated that the optimal column possessed good mechanical stability and high permeability. The adsorption capacities of the optimized monolithic column for perfluorooctanoic acid and perfluorooctane sulfonate were 0.257 and 0.513 μg/mg, respectively. Adsorption capacities of the monoliths were proved to increasing with increasing the amounts of fluorinated monomers in the fluorous monoliths. Sodium 1-octanesulfonate, as a comparison compound, was hardly adsorbed on the fluorous monolith. In addition, the trace amounts of perfluorooctanoic acid and perfluorooctane sulfonate in water samples can be successfully concentrated about 160 times to their original concentrations by this monolithic column. These results demonstrated that the capacity and selectivity of the affinity fluorous column is high and can be applied to the selective enrichment for the perfluorinated persistent organic pollutants from environmental samples.