The unique minerals of the Au-Pd-Hg system in gold grains from heavy concentrates of the Itchayvayam placers and watercourses draining and ore samples of the Barany outcrop at the Itchayvayam mafic–ultramafic complex (Kamchatka, Russia) were investigated. Gold grains from watercourses draining and heavy concentrates of the Itchayvayam placers contain substitution structures formed by Pd,Hg-rich low-fineness gold (Au0.59–0.52Pd0.24–0.25Hg0.17–0.23, 580‰–660‰) and Pd,Hg-poor high-fineness gold (Au0.94–0.90Pd0.02–0.04Hg0.03, 910‰–960‰). Potarite (PdHg) without and with impurities (Au < 7.9, Cu < 3.5, Ag < 1.2 wt.%), Ag-poor high-fineness gold (Au0.91Ag0.09, 950‰), Ag,Pd,Hg-bearing middle-fineness gold (Au0.75Ag0.08Pd0.09Hg0.08—Au0.88Ag0.09Pd0.02Hg0.01, 820‰–930‰), and Pd,Hg-rich low-fineness gold with minor contents Ag and Cd (Au0.51–0.55Pd0.25–0.22Hg0.21–0.16Ag0.03–0.06Cd0.01, fineness 580‰–630‰) were observed as individual microinclusions in the ore samples of the Barany outcrop. XRD and EBSD study results show that the Pd,Hg-rich low-fineness gold is isotypic to gold and has the same structure type, but different cell dimensions. According to data obtained for the Itchayvayam and some deposits and ore occurrences with Pd,Hg-bearing gold, the stable ternary phases and solid solutions of the following compositions in the Au-Pd-Hg system have been identified: Pd,Hg-poor gold (Au0.94–0.90Pd0.02–0.04Hg0.03), Pd,Hg-rich gold (Au0.59–0.52Pd0.24–0.25Hg0.17–0.23), Au-potarite (PdHg0.62Au0.38—Pd1.04Hg0.96—Au0.80Pd0.68Hg0.52), and Au,Hg-bearing palladium (Pd0.7Au0.3Hg0.1). The genesis of Pd,Hg-rich gold is insufficiently studied. We supposed that the meteoric waters or low-temperature hydrotherms rich in Pd and Hg could lead to the replacement Pd,Hg-poor gold by Pd,Hg-rich gold. High concentrations of Pd in Pd,Hg-bearing gold indicate a genetic relationship with mafic–ultramafic rocks.