Three porous organic frameworks (POFs) were synthesized by the reaction between phloroglucinol and 1,4-phthalaldehyde, 4,4 '-biphenyldialdehyde or tris-(4-formylphenyl) amine; the products are named as POF-a, POF-b and POF-c, respectively. They were used to prepare POFs coated stir bars respectively for the extrac-tion of four carbamate pesticides (CMPs). POF-c coated stir bar exhibited better adsorption performance than POF-a/b coated stir bar and commercial stir bars, probably due to the stronger conjugated structure and hy-drophobicity of POF-c, and resultant hydrophobic, pi-pi and hydrogen bonding interactions between them. The adsorption mechanism for target CMPs was verified by characterization techniques and molecular dynamics simulation. A method of POF-c coated stir bar sorptive extraction-high performance liquid chromatography -variable wavelength ultraviolet detector was developed for the analysis of four CMPs in corn and potato sam-ples. Under the optimal conditions, LODs of the method were between 0.017 and 0.048 mu g/L, and the linear range for four CMPs was 0.1/0.2-200 mu g/L.