To improve the adsorption selectivity towards hexavalent chromium anion (Cr(VI)), surface Cr(VI)-imprinted polypropylene (PP) fibers were fabricated by the plasma-mediated grafting strategy. Hence, a non-thermal Rradio frequency discharge plasma irradiation followed by a gaseous phase grafting was used to load acrylic acid (AA) onto PP fibers, which was afterwards amidated with triethylenetetramine and subjected to imprinting with a Cr(VI) template. The plasma irradiation conditions, i.e., gas species, output power, pressure, and time, were optimized and then the influence of grafting time, pressure, and temperature on the grafting degree of AA was investigated. Scanning electron microscopy and Fourier transform infrared spectroscopy were used for the characterization of pristine and modified fibers and to confirm the synthesis success. The hydrophilicity of modified fibers was greatly improved compared with pristine PP fibers. The adsorption thermodynamics and kinetics of Cr(VI) were investigated, as well as the elution efficiency and reusability. The prepared imprinted fibers showed superior adsorption selectivity to Cr(VI) compared with non-imprinted fibers. Finally, the stability of the imprinted fibers against the oxidation ability of Cr(VI) is discussed.