Sludge is an integral part in the migration pathway of silver nanoparticles (AgNPs) from manufacture to the terrestrial environment. However, the detailed information on the role of natural organic matters (NOMs) remains limited. In this study, the sludge generated from coagulation of wastewater spiked with AgNPs (denoted as sludge) was taken as the model. Effects of humic acid (HA), alginate (AA) and bovine serum albumin (BSA) on the release amount, dynamics and speciation of silver from the sludge were investigated by a series of leaching experiments. The results showed that HA, AA and BSA in the leaching solution could enhance the silver release from the sludge. The concentrations of the dissolved and colloidal silver in the BSA solution were the highest at the initial stage of dynamic leaching. The controlling step of the silver release was internal diffusion in the HA and AA solution, while the release of dissolved silver was controlled by both chemical reaction and internal diffusion in the BSA solution. In addition, the released colloidal silver fractions in the BSA solution contained more particles with size >50 nm compared with the HA and AA solutions. The results suggested that the properties of NOMs may be the key factor affecting the transfer of AgNPs from the sludge to the terrestrial environment.