In this study, a new adsorbent based on monolith/aminated carbon nanotubes composite was facilely prepared and employed as the extraction phase of multiple monolithic fibers solid-phase microextraction for the capture of phenoxycarboxylic acids herbicides. The adsorbent was fabricated by mingling aminated carbon nanotubes in the poly (allylthiourea-co-ethylene glycol dimethacrylate) monolith. Various techniques were employed to characterize the morphology, structure, and pore size of the prepared adsorbent. The proposed microextraction method displayed satisfactory capture performance towards studied analytes through multi-interactions such as hydrogen-bonding, hydrophobic and π-π interactions. Under the optimized conditions, a sensitive and reliable method to quantify trace analytes in water and soil samples was developed. The limits of detection were in the ranges of 0.13-0.25 μg/L and 0.20-0.61 μg/kg for water and soil samples, respectively. The practicality of the introduced method was demonstrated by applying it to monitor the contents of studied analytes in environmental water and soil samples. Satisfactory fortified recoveries (76.4-119%) and reproducibility were obtained. The achieved results well demonstrated that the suggested microextraction technique can efficiently extract phenoxycarboxylic acids and the developed method exhibits a promising potential for reliable and sensitive quantification of trace analytes in complex samples.