We present a simple hot injection method for the preparation of colloidal solutions of hydrophobic spherical gold nanoparticles with the diameter around 20 nm and size dispersion below 20%. Various surfactants with different lengths of hydrocarbon chains, such as oleylamine, 1-octadecanethiol, poly (N-vinylpyrrolidone), and AgNO3 in 1,5-pentanediol, were used for sterical stabilization in the colloidal solution. The hydrodynamic nanoparticle size and size dispersion were determined by the dynamic light scattering (DLS) while the small-angle X-ray scattering (SAXS) from the colloidal solution provided information on the size of the metallic nanoparticle core (without surfactant). Plasmon enhanced resonant absorption peaks between 500 nm and 600 nm were detected by the UV-VIS spectrophotometry. The nanoparticle arrays on silicon prepared by solvent evaporation or Langmuir-Schaefer method were inspected by high-resolution scanning electron microscopy and grazing-incidence SAXS (GISAXS). The presence of side maxima in the GISAXS pattern gives evidence of the nanoparticle ordering by self-assembly while very close values of the interparticle distance derived from GISAXS and the nanoparticle size derived from DLS indicate a close-packed order.