A novel Cr(VI) ion imprinted polymer (IIP) was proposed for fast removal of Cr(VI) from aqueous solution. 4-Vinylpyridine and N,N-diethylaminoethyl methacrylate were used as functional monomers, and ethylene glycol dimethacrylate and 2,2-azoisobisbutyronitrile were used as cross-linker and initiator in the presence of a binary porogenic solvent. The prepared Cr(VI)-IIPs were characterized by the Fourier transform infrared spectroscopy and scanning electron microscopy. The effects of pH, initial concentration of Cr(VI) in aqueous solution, temperature, and operating time on adsorption were investigated. At the low pH range of 1.5-2.5, the adsorption capacities were high. The influence of temperature was slight. The adsorption equilibrium time was within 3 min. The adsorption process followed the pseudo-second-order equation and the Langmuir isotherm model. The maximum adsorption capacity was up to 286.56 mg/g, and the selectivity factors of Cr(VI)/Cu(II), Cr(VI)/Cd(II), and Cr(VI)/Cr(III) were up to 135.78, 145.44, and 69.91, respectively.