The effects of silver nanoparticles (Ag NPs) on the soil environment have attracted considerable research attention. Previous studies mainly focused on agent‐coated Ag NPs, which inevitably introduce additional disturbance of chemical agents to the intrinsic property of Ag NPs. We investigated the environmental effects induced by pure surfactant‐free Ag NPs (SF‐Ag NPs), including soil enzyme activities (urease, sucrase, phosphatase, and β‐glucosidase), bacterial community structure, and functional profile, over different exposure periods in the present study. The results indicated that these enzymes, especially urease and phosphatases, exhibit different responses to SF‐Ag NPs and are more susceptible to SF‐Ag NPs than other enzymes. Surfactant‐free Ag NPs can also induce a decrease in bacterial diversity and a change of bacterial community structure. The abundance of SF‐Ag NPs in Proteobacteria increased, but decreased in Acidobacteria after 14 days of exposure. Moreover, the abundance of genus Cupriavidus was significantly higher than those of the respective controls. By contrast, SF‐Ag NP exposure for 30 days could attenuate these negative effects. The phylogenetic investigation of communities by reconstruction of unobserved states (PICRUSt) prediction revealed that SF‐Ag NPs exert a negligible effect on bacterial function, thereby suggesting that functional redundancy is conduced to bacterial community tolerance to SF‐Ag NPs. These findings will help us further understand the environmental toxicity of Ag NPs. Environ Toxicol Chem 2023;42:1685–1695. © 2023 SETAC