This paper describes the infl uence of the chain length and the functional group steric accessibility of thiols modifi ers on the phase transfer process effi ciency of water synthesized gold nanoparticles (AuNPs) to toluene. The following thiols were tested: 1-decanethiol, 1,1-dimethyldecanethiol, 1-dodecanethiol, 1-tetradecanethiol and 1-oktadecanethiol. Nanoparticles (NPs) synthesized in water were precisely characterized before the phase transfer process using Atomic Force Microscopy (AFM) and Transmission Electron Microscopy (TEM). The optical properties of AuNPs before and after the phase transfer were studied by the UV-Vis spectroscopy. Additionally, the particle size and size distribution before and after the phase transfer of nanoparticles were investigated using Dynamic Light Scattering (DLS). It turned out that the modifi cation of NPs surface was not effective in the case of 1,1-dimethyldecanethiol, probably because of the diffi cult steric accessibility of the thiol functional group to NPs surface. Consequently, the effective phase transfer of AuNPs from water to toluene did not occur. In toluene the most stable were nanoparticles modifi ed with 1-decanethiol, 1-dodecanethiol and 1-tetradecanethiol.