The 4-nitrophenol imprinted materials that can selectively identify and remove 4-nitrophenol pollutants were prepared by surface imprinting and sol?gel methods using 4-nitrophenol as template molecule, α-methacrylic acid (α-MAA) as functional monomer, three hydroxymethyl propane three methacrylate (TRIM) as crosslinking agent, 2-methylpropionitrile (AIBN) as initiator. The effects of mole ratios of 4-nitrophenol to α-MAA and 4-nitrophenol to TRIM, types of pore formation agents and extracting solutions on the adsorption properties of surface molecularly imprinted materials were investigated. The preparation conditions of imprinted materials were further optimized by orthogonal experiments. The imprinted materials synthesized under the optimum conditions were characterized by scanning electron microscope, Fourier transform infrared spectroscopy, specific surface analyzer, thermo-gravimetric analyzer and nanometer particle size analyzer. The results showed that the imprinted material had the best removal efficiency to 4-nitrophenol when the molar ratio of 4-nitrophenol to α-MAA and 4-nitrophenol to TRIM were 1:8 and 1:10, respectively, the pore formation agent was ethanol and the extracting solution was methanol/acetic acid (7:3, volume ratio), the value was 6.23 μmol/g. 4-nitrophenol was successfully imprinted on the surface of silica gel and the imprinted materials could specifically adsorb 4-nitrophenol.