AbstractElectron microprobe analysis (EMPA), X‐ray powder diffraction (XRD), and Raman spectroscopy (RS) were applied to characterize the synthetic gold chalcogenides of the Au–Te–Se–S system and natural analogs from the Gaching deposit (Central Kamchatka, Russia). The EPMA results showed that the synthetic chalcogenides have different Te/Se/S and Au/X (X = Te + Se + S) ratios: AuX2, Au3X10, and AuX. They are similar in composition to natural compounds — calaverite (AuTe2), maletoyvayamite (Au3Te6Se4), and unnamed minerals AuTe0.7Se0.3 and AuSe0.7S0.3. It was established that chalcogenides AuX, Au3X10, and AuX2 have a specific Raman spectra with characteristic peaks. The position of the peaks and the character of the spectra of the synthetic phases and their natural analogs from the Gaching deposit coincide within the limits of accuracy. Different ratios of chalcogenes Te/Se/S in compounds influence the Raman peak positions. The positions of the peaks for natural compounds AuX differ depending on the predominance of Te (AuTe0.7Se0.3) or Se (AuSe0.7S0.3). AuSe synthetic phases consist of a mixture of α‐ and β‐polymorphs. Raman spectroscopy can be used for the identification of natural gold chalcogenides worldwide, which are difficult to diagnose by other methods due to the microscopic grain sizes and close intergrowths with other ore minerals. The similarity of the Raman spectra upon changing the concentrations of Se and S suggests identical structures and possible isomorphism in the composition range of AuTe0.7Se0.3– AuTe0.7Se0.2S0.1, AuTe1.9Se0.1– AuTe1.8Se0.1S0.1, and Au3Te6Se4– Au3Te6S3Se.