Two new liquid dimethylgold(III) complexes (with substituted dithiophosphinate) of the general formula Me2AuS2PX2 (in 1, X = OMe and in 2, X = OEt), as well as their synthesis and thermal behavior, are reported. The compounds are stable under storage, do not require special handling conditions, and they exhibit a good volatility and vaporization stability. The decomposition of the vapor of these compounds on the surface is observed to begin at T = 433 K (160°C) for 1 and 423 K (150°C) for 2. The decomposition pathways to elemental gold are established, based on the temperature dependences of the gas-phase composition. The formation of gold films using metal-organic (MO)CVD within the temperature range 483 − 523 K (210 − 250°C) is confirmed by means of X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analysis.