This work investigates the performance of the nickel sulfide fire assay (NiS-FA) for the pyrometallurgical analysis of platinum group elements (PGEs) from mixtures of automotive exhaust catalytic converters (e.g., gasoline, diesel, and diesel particular filter) by assessing the effects of various flux materials and reaction parameters on platinum, palladium, and rhodium recovery. Inductively coupled plasma mass spectrometry and atomic absorption spectroscopy (AAS) are used for the analysis of the NiS-FA beads. We found that the optimum recovery (at least 99.0%) was achieved with reaction of 11.5 g of flux (0.53w/w ratio, sodium tetraborate: sodium carbonate), 1 g nickel, and 0.84 g sulfur (1.2w/w ratio, Ni:S) per gram of sample for 90 min at 975 degrees C. Reference standards (NIST SRM 2557) were used to compare efficiencies and identify the optimum conditions. The results are consistent with certified values and PGEs could be recovered within the 95% confidence level. The precision (<4.0% RSD) of all measurements, expressed as percentage relative standard deviation (SD), ranged up to 3.0%.