Density functional calculations on the ground state geometries and stabilities of PdOn species (n = 1–5) are performed in neutral as well as anionic forms. Calculations reveal that Pd can bind stably with four O atoms indicating the maximum oxidation state of Pd as high as +8. The electron affinities of PdOn suggest that these species behave as superhalogens for n ≥ 2. The large electron affinities of PdOn species along with stability of their anions point toward the synthesis of new class of compounds having unusual oxidizing capabilities. This possibility is explored by considering the interaction of PdO2 superhalogen with Ca atom which forms a stable CaPdO2 complex. In this complex, PdO2 unit closely mimics the behavior of O atom when compared with CaO molecule. © 2013 Wiley Periodicals, Inc.