The reaction products of palladium atoms with molecular oxygen in solid argon have been investigated using matrix isolation infrared absorption spectroscopy and quantum chemical calculations. In addition to the previously reported mononuclear palladium–dioxygen complexes: Pd(η 2 –O 2 ) and Pd(η 2 –O 2 ) 2 , dinuclear palladium–dioxygen complexes: Pd 2 (η 2 –O 2 ) and Pd 2 (η 2 –O 2 ) 2 were formed under visible light irradiation and were identified on the basis of isotopic substitution and theoretical calculations. In addition, experiments doped with xenon in argon coupled with theoretical calculations suggest that the Pd(η 2 –O 2 ), Pd 2 (η 2 –O 2 ) and Pd 2 (η 2 –O 2 ) 2 complexes are coordinated by two argon or xenon atoms in solid argon matrix, and therefore, should be regarded as the Pd(η 2 –O 2 )(Ng) 2 , Pd 2 (η 2 –O 2 )(Ng) 2 and Pd 2 (η 2 –O 2 ) 2 (Ng) 2 (NgAr or Xe) complexes isolated in solid argon.