Combined structural and chemical characterization of cationic polynuclear palladium coordination compounds Pd₅₆₁L₆₀(OAc)₁₈₀, where L=1,10-phenantroline or 2,2′-bipyridine has been carried out by high-resolution electron microscopy (HREM) and analytical electron microscopy methods including electron energy-loss spectroscopy (EELS), zero-loss electron spectroscopic imaging, and energy-dispersive X-ray spectroscopy (EDX). The cell structure of the cluster matter with almost completely uniform metal core size distributions centered around 2.3 ±0.5 nm was observed. Zero-loss energy filtering allowed to improve the image contrast and resolution. HREM images showed that most of the palladium clusters had a cubo-octahedral shape. Some of them had a distorted icosahedron structure exhibiting multiple twinning. The selected-area electron diffraction patterns confirmed the face centered cubic structure with lattice parameter close to that of metallic palladium. The energy-loss spectra of the populations of clusters contained several bands, which could be assigned to the delayed Pd M_{4, 5}-edge at 362 eV, the Pd M₃-edge at 533 eV and the Pd M₂-edge at 561 eV, the NK-edge at about 400 eV, the O K-edge at 532 eV overlapping with the Pd M₃-edge and the carbon C K-edge at 284 eV. Background subtraction was applied to reveal the exact positions and fine structure of low intensity elemental peaks. EELS evaluations have been confirmed by EDX. The recorded series of the Pd M-edges and the N K-edge in the spectra of the giant palladium clusters obviously were related to Pd-Pd- and Pd-ligand bonding.