Sorption and cosorption of the nonionic herbicide mefenacet and two typical metals (copper and silver) on black soil and its components (kaolinite and humic acid) were investigated. It was found that because of their different valences and properties, Cu2+ and Ag+ presented different effects on the sorption of mefenacet. Due to the competition of Cu2+, along with the shells of dense water formed by its surface complexation, for sorption surface area with mefenacet, the addition of Cu2+ decreased the sorption amount of mefenacet on soil and its components, especially on humic acid. However, the addition of Ag+ significantly enhanced the sorption of mefenacet, which was attributed to the softness of the cation that weakened the hydrophilicity of the local region around Ag(+)-complexed functionalities, and thus mitigated the competitive sorption of water. In addition, the sorption of mefenacet on soil with or without the two metals was generally decreased with increasing pH, which was caused by the hydrolysis of carbonyl and carboxyl groups on the surface of the sorbents, pi-pi interaction between mefenacet and the soil organic matter, and so on. On the other hand, the presence of mefenacet seemed to have little effect on the sorption of Cu2+ and Ag+, indicating that Cu2+ and Ag+ might be sorbed strongly on the tested sorbents and the mefenacet added was too low in concentration to affect the sorption of the metals.