The primary object of this contribution is to self-assemble DNA on 2-dimensional array of 1-dodecanethiol-encapsulated colloidal gold (2-DACG). The 2-DACG film was deposited by Langmuir-Blodgell (LB) technique. Through phase transfer of aqueous colloidal gold particles into ethanol solutions containing 1-dodecanethiol, the hydrophobic gold colloidal nanoparticles were accomplished. In the presence of traces of 1-dodecanethiol, the gold nanoparticels were transferred via LB technique to a freshly cleaned gold electrode and 2-DACG of close-packed, ordered monolayer was obtained. The 2-DACG was then used as a substrate for the immobilization of DNA under a controled potential of 0.20V vs. saturated calomel electrode (SCE). The properties of 2-DACG before and after the DNA assembly were investigated by means of transmission electron microscopy (TEM), atomic force microscopy (AFM), cyclic voltaininetry (CV) and electrochemical impedance spectroscopy (EIS). The results indicated that 2-DACG deposited by LB technique was suitable as a substrate for DNA self-assembly.