To establish the dissolution mechanism of palladium (Pd) in the Fe t O–SiO 2 –CaO–Al 2 O 3 –MgO sat slag system, the Pd solubility was measured at 1873 K (1600 °C) and oxygen partial pressure ranging from p O 2 = 1.0 × 10 - 8 atm to p O 2 = 1.0 × 10 - 6 atm . In the current slag system, the Pd solubility increases with increasing content of CaO and FeO, and decreases with increasing content of SiO 2 and Al 2 O 3 . This solubility behavior is quantified by employing the modified Vee ratio, defined as (CaO+FeO)/(SiO 2 +Al 2 O 3 ), the theoretical optical basicity and the activity of CaO in the slag. Thermodynamic analysis reveals that Pd stabilizes in the form of the ( PdO 2 3 - ) palladate complex ion in the present aluminosilicate melts. Based on this, the Pd dissolution reaction in the current slag system is proposed as follows: Pd ( l ) + 1 4 O 2 ( g ) + 3 2 O 2 - = ( PdO 2 3 - ) Combining the results from the present experiment and previous findings suggests that a well-designed slag system can effectively minimize Pd loss during the pyrometallurgical processing of industrial wastes containing Pd. By adjusting the modified Vee ratio, in which CaO and FeO promote Pd solubility in the slag, whereas SiO 2 increases slag viscosity, it is possible to achieve optimal conditions. Therefore, we recommend implementing such an optimized slag system for pyrometallurgical treatment of Pd-containing industrial wastes, ensuring minimal Pd loss and maximizing resource recovery.