The water-insoluble title compound, octakis(mu-acetato-kappa2O:O)octakis(mu-nitroso-kappa2N:O)octapalladium(II), [Pd8(CH3COO)8(NO)8], was precipitated as a yellow powder from a solution of palladium nitrate in nitric acid by adding acetic acid. Ab initio crystal structure determination was carried out using X-ray powder diffraction techniques. Patterson and Fourier syntheses were used for atom locations, and the Rietveld technique was used for the final structure refinement. The crystal structure is of a molecular type. The skeleton of the [Pd8(CH3COO)8(NO)8] molecule is constructed as a tetragonal prism with Pd atoms at the vertices. The eight NO- groups are in bridging positions along the horizontal edges of the prism. The N and O atoms of each nitroso group coordinate two different Pd atoms. The vertical edges present PdPd contacts with a short distance of 2.865 (1) A. These Pd atoms are bridged by a pair of acetate groups in a cis orientation with respect to each other. The complex has crystallographically imposed 4/m symmetry; all C atoms of the acetate groups are on mirror planes. The unique Pd atom lies in a general position and has square-planar coordination, consisting of three O and one N atom.