Multiwalled carbon nanotubes with exceptional merits as SPE adsorbents for enrichment of environmental pollutants have absorbed much attention. The goal of this paper was to make a comparison with it and regular adsorbents such as C18 silica and activated carbon in the extraction capacity of atrazine and simazine. The results indicated that multiwalled carbon nanotubes were very suitable for determination of atrazine and simazine because of an enrichment performance similar to that of C18 silica. In contrast, the spiked recovery of simazine was higher than that of atrazine using multiwalled carbon nanotubes as packing material for SPE. However, reverse results were obtained when the extraction was performed with packing of C18 silica. Moreover, as the extraction of simazine was concerned, multiwalled carbon nanotubes were much better than C18 silica. As for the enrichment of atrazine, C18 silica achieved greater extraction factor than multiwalled carbon nanotubes. Activated carbon did not give the expected extraction efficiency because of its large size and blank volume and less active sites for adsorption. All these experimental results indicated that multiwalled carbon nanotubes could be used as a valuable alternative adsorbent for SPE of atrazine and simazine in many real water samples.