Abstract: Quaternary chalcogenides of AuX (AuTe0.7Se0.2S0.1), Au3X10 (Au3Te6Se3S, Au3Te6Se2.5S1.5), and AuX2 (AuTe1.8Se0.2, AuTe1.8Se0.1S0.1) composition were synthesized for the first time in the Au‒Te‒Se‒S system, where Te ≥ Se + S. They are produced by dry synthesis upon heating a mixture of elementary substances with compositions of AuTe0.666Se0.167S0.167 (X/Au = 1, X = Σ(Te + Se + S)), AuTeSe0.5S0.5 (X/Au = 2), AuTe2Se1.125S0.375, AuTe2Se0.75S0.75 (X/Au = 3.5), and AuTe2.5SeS0.5 (X/Au = 4) in vacuum quartz ampoules from 25–700°C and annealing at 400°C. According to XRD, the synthetic Au chalcogenides of AuTe1.8(Se,S)0.2 composition correspond to calaverite (α-AuTe2). The unidentified XRD peaks belong to AuX and Au3X10. They are synthetic analogs of previously unknown natural compounds, which were found in the Gaching area of the Maletoivayam ore field (Central Kamchatka volcanic belt). The compositions of natural phases span the following ranges: Au0.99–1.00Te0.70–0.71Se0.25–0.27S0.03–0.06 and Au2.91–3.08Te5.85–6.06Se1.57–3.66S2.63–0.44. The Raman spectra of synthetic and natural Au chalcogendies close in composition are identical.