In this study, organic aerogels were synthesized by the sol-gel polycondensation of mixed cresol with formaldehyde in a slightly basic aqueous solution. Carbon aerogels and xerogels are generated by pyrolysis of organic aerogels. The novel sol-gel-based micro-solid-phase extraction sorbent, resorcinol-formaldehyde xerogel, was employed for preconcentration of some selected herbicides. Three herbicides of the aryloxyphenoxypropionate group, clodinafop-propargyl, haloxyfop-etotyl, and fenoxaprop-P-ethyl, were extracted from aqueous samples by micro-solid-phase extraction and subsequently determined by gas chromatography with mass spectrometry. The effect of different parameters influencing the extraction efficiency of these herbicides including sample flow rate, sample volume, and extraction time were investigated and optimized. Under optimum conditions, linear calibration curves in the range of 0.10-500 ng/L with R(2) > 0.99 were obtained. The relative standard deviation at 50 μg/L concentration level was lower than 10% (n = 5) and detection limits were between 0.05 and 0.20 μg/L. The proposed method was successfully applied to the sampling and extraction of herbicides from Zayanderood and paddy water samples.