The metal source and ore precipitation mechanism of orogenic gold mineralization are not yet well understood, partly because ore metals may be derived from different sources. Pyrite is a dominant Au-hosting mineral in the Ashawayi orogenic gold deposit in the southwestern Tianshan orogen, western China. Petrographic features of pyrite in host rocks and orebodies define four generations: diagenetic preore (Py1), hydrothermal early-ore (Py2), main-ore (Py3), and late-ore (Py4) pyrites. Trace element abundances were analyzed in situ by femtosecond laser ablation inductively coupled plasma mass spectrometry (fs-LA-ICP-MS) to unravel the pyrite formation history. Preore Py1 contains the lowest Cu, Mo, Se, Au and As contents, consistent with a diagenetic origin. Py2 has higher Au and As contents than Py1 and may have formed by the reaction between hydrothermal fluid and preexisting Py1, as indicated by diagenetic pyrite-like As/Ni and Bi/Au ratios but lower hydrothermal pyrite-like Sb/Au ratios in Py2. Hydrothermal pyrite (Py3) contains more abundant As (1723–65182 ppm) and Au (0.32–107 ppm) but lower Co and Ni contents than Py2, suggesting a greater hydrothermal fluid contribution. Oscillatory zoning and abundant mineral inclusions (e.g., arsenopyrite and chalcopyrite) in porous Py3 indicate that fluid boiling was responsible for gold deposition during the main-ore stage. Py4 is a relict of hydrothermal pyrite (Py3) but not diagenetic pyrite, as supported by Py4 and Py3 clustering into a class based on hierarchical cluster analysis. The application of a machine learning method (i.e., artificial neural network) to the syn-ore pyrite indicates that the Ashawayi gold deposit has affinity to those from orogenic-type gold deposits worldwide. Our study, therefore, highlights that ore metals in orogenic gold deposits may originate from different sources, such as Au and As, which are largely sourced from metamorphic fluids, while Co and Ni are mainly released from preore sedimentary pyrite, fluid boiling and fluid-rock interaction triggered precipitation of Au and other metals.