The mineralogy and chemical composition of native gold from twenty-seven representative orogenic gold deposits were investigated using optical microscopy, electron probe microanalysis (EPMA), and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Minor elements, such as Ag and Cu, occur in solid solution, while trace elements, such as Fe, As, S, Hg, form impurities or micro inclusions in native gold. Partial least squares-discriminant analysis (PLS-DA) has identified compositional characteristics based on mineral association, gold texture and dominant country rocks. Gold grains are commonly associated with pyrite, arsenopyrite, chalcopyrite, pyrrhotite, and tourmaline in the studied orogenic deposits. Chemical variations in gold with different associated mineral assemblages are related to the partitioning of trace elements between co-crystalizing minerals and gold during precipitation. Gold inclusions in gangue minerals are discriminated from later gold in fractures based on contents of Ag, Fe, Pb, and Bi, which indicates that gold in different paragenetic stages of mineralization can be identified using its trace element signature. Gold hosted in different regional country rocks can be discriminated by Ag, Cu, Pd, Sb, and Hg, likely because of reactions of hydrothermal fluids with the regional country rocks along the fluid flow paths.