This paper describes the influence of the chain length and the functional group steric accessibility of thiols modifiers on the phase transfer process efficiency 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 modification of NPs surface was not effective in the case of 1,1-dimethyldecanethiol, probably because of the difficult 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 modified with 1-decanethiol, 1-dodecanethiol and 1-tetradecanethiol.