Using metal-organic (MO)CVD, gold films and arrays of gold nanoparticles are obtained from volatile organometallic dimethylgold(III) complexes with O, N, S donor ligands. As precursors, such compounds as (CH3)2Au(OAc), (CH3)2Au(piv), (CH3)2Au(OQ), (CH3)2Au(SQ), (CH3)2Au(thd), and (CH3)2Au(dtc) were used. Deposition processes are carried out within a low pressure (LP)CVD reactor with additional vacuum ultraviolet (VUV) stimulation, with and without a hydrogen reactant gas. The influence of precursor structure on the morphology of the deposited layers is demonstrated. The use of precursor (CH3)2Au(OQ) results in obtaining ultra-thin continuous gold film ∼3 nm thick. It is established that with hydrogen reactant gas injected into the system, the amount of impurities in the film decreases. With the VUV stimulation, the gold content in the films amounts to almost 100%; in addition, the morphology of coatings is observed to change significantly. According to the X-ray diffraction (XRD) phase analysis, gold crystallites in the films grow mainly in the  direction.