The paper presents the research results on synthesizing silver nanoparticles in aqueous solutions and their extraction into the organic phase. Studies have shown that it is best to perform the extraction process using n-hexane > cyclohexane > toluene > chloroform > ethyl acetate. The results show a correlation between the dielectric constant of the organic phase and its ability to extract nanoparticles. The lower the dielectric constant is, the higher the extractability. The hydrodynamic radius of the silver nanoparticles changes after transfer to the organic phase, depending greatly on the organic phase used. The extraction mechanism is complex and multi-step. As the first step, the Ag nanoparticles are transferred to the phase boundary. As the second step, the octadecylamine (ODA) molecules adsorb on the silver nanoparticles (AgNPs) surface. The change in particle shape was also noted. This suggests that the interfacial processes are more complex than previously reported. Below the initial concentration of ODA 2 × 10−4 M, the formation of a third phase has been observed. In a one-stage experiment, the concentration of silver nanoparticles after transferring to the organic phase was increased 500 times in about 10 s. The role of the concentration of ODA, therefore, is not only a measure of the extraction efficiency and productivity but functions as an enabler to maintain favorable biphasic processing, which underlines the role of the solvent again.