•A pyrazosulfuron-ethyl imprinted polymer with hydrophilic external layers was synthesized.•Reversible addition–fragmentation chain transfer polymerization was used in synthesis.•Polyethylene glycol was used as porogen in the precipitation polymerization.•Online SPE/HPLC for sulfonylurea residue analysis from soil samples was established.A new bifunctional pyrazosulfuron-ethyl imprinted polymer was synthesized by the combination of molecular imprinting technology and living radical polymerization. In the synthesis, the pyrazosulfuron-ethyl imprinted polymer was obtained by the reversible addition–fragmentation chain transfer (RAFT) precipitation polymerization followed by grafting poly(glyceryl monomethacrylate) (pGMMA) by the post-RAFT polymerization. In this research, we used polyethylene glycol (PEG) as the polymeric porogen in order to increase the porosity of the material which is a new porogen application in the precipitation polymerization. The imprinted polymer has selectivity for the template and ability of humic acids exclusion which has shown the merits of molecularly imprinted polymers and restricted access materials. An online solid-phase extraction/HPLC method for the analysis of three sulfonylurea residues in soil samples has been developed and validated. The recovery of 81–99% in the spiked levels of 40–200 μg kg−1 was obtained and the limit of detection (LOD) and limit of quantification (LOQ) were less than 4.8 and 15.9 μg kg−1 respectively. The results demonstrated that this bifunctional material can be used for the efficient pyrazosulfuron-ethyl extraction in the sulfonylurea residue analysis from environmental samples.