Abstract The Baimazhai deposit in Yunnan Province is one of the largest Cu–Ni sulfide deposits hosted in mafic–ultramafic intrusions in China. Concentrations of platinum-group elements (PGE) in massive sulfide ores and host rocks from Baimazhai were determined by using inductively coupled plasma mass spectrometry (ICP-MS) following nickel sulfide fire assay pre-concentration. The results show that the total PGE (ΣPGE) are quite low, decreasing gradually from central massive ores (78.2–556 ppb) to olivine pyroxenite (0.472–67.0 ppb), gabbro (0.847 ppb) and, websterite (0.76–0.809). The intruded lamprophyre dykes also show low ΣPGE (2.98–4.07 ppb). The ΣPGE exhibit obvious positive correlations with Au, Ni and Cu contents. Primitive mantle normalized PGE patterns of the massive Cu–Ni ores are of the Pt–Pd type with relatively steep and trough-like patterns, which are similar to those of the host rocks. In addition, the Pt/Pd and Cu/Pd ratios of the massive sulfide ores are similar to those of olivine pyroxenite, gabbro and websterite. These characteristics suggest that sulfides in the massive ores are of magmatic origin, co-genetic with their host rocks. The relatively high Pt/Pd ratios of the Baimazhai massive sulfide ores (averaging 0.83) and their host rocks imply that the Baimazhai sulfides formed in a single sulfide saturation event, but not through multiple sulfide injections. High Ir contents (0.77–5.52 ppb, averaging 2.35 ppb) and dramatically variable Pd/Ir ratios (4.76–296, averaging 138) of the massive sulfide ores suggest that the Baimazhai sulfide ores might have suffered significant late stage hydrothermal alteration. The Baimazhai massive sulfide ores yield a Re–Os isochron age of 259 ± 20 Ma (MSWD = 0.025), which is the same as the major eruption stage of the Emeishan large igneous province and the Baimazhai intrusion, further supporting their magmatic origin. The initial 187Os/ 188Os value of 0.456 ± 0.026 indicates that crustal contamination has played an important role during mineralization. The proportion of crust-derived Os is calculated to be more than 30%.