A petrographic investigation of ore samples from the Assarel porphyry copper deposit in the Srednogorie metallogenic zone (Bulgaria) constrains the setting and character of precious metals (Au, Ag, PGE) and related minerals within the deposit. This work supports renewed interest in understanding the deportment of precious metals and provides mineralogical knowledge during the testing and validation of novel drill core 3D X-ray computed tomography–X-ray fluorescence (XCT-XRF) scanning technology being developed as part of the X-MINE project. Scanning electron microscopy–energy dispersive spectrometry (SEM-EDS) results indicate precious metals occur in their native state (Au, Ag), as sulfides (Ag), sulfosalts (Au), tellurides (Ag, Pd), and selenides (Ag), and typically form micron-sized inclusions in pyrite and chalcopyrite or are disseminated in the groundmass of the rock. Preservation of early Fe oxide–chalcopyrite ± bornite assemblage as relics in the more dominant pyrite-chalcopyrite mineralization assemblage supports mineral disequilibrium relationships and multi-stage mineralization events. Several rare minerals (e.g., merenskyite, acanthite, sorosite, tetra-auricupride, auricupride, greenokite, bismuthinite, nagyagite, native Ni) are reported for the first time at Assarel and highlight the mineralogical diversity of the ore. The occurrence of precious metals and related minerals at Assarel attest to a complex hydrothermal system that underwent progressive physicochemical changes during the evolution of the mineralizing system (e.g., redox conditions, fluid chemistry).