In this work an improved synthetic route that exploits a quaternary water-in-oil microemulsion has been used to obtain nanocrystals of ZnS, CdS and their mixed compounds, - CdxZn1-xS - differing by their size and composition and having high crystalline quality, small dimensions and a quite good size distribution. The opportunity offered by the use of water-in-oil microemulsion to immobilize the nanocrystals onto solid substrate by self-assembling to obtain stable adherent layers has also been exploited. The physical and chemical properties of obtained nanocrystals and layers have been investigated by UV-vis spectroscopy, X-Ray Diffraction X-ray Photoelectron Spectroscopy and Scanning Tunneling Microscopy. The role played by the co-surfactant (pentanol) in controlling nanocrystal size and stability has been discussed.