A series of salts (R4N)(2)[Pd(NO3)(4)] (R = CH3, C2H5, n-C3H7; 1-3) were synthesized in high yield from a nitric acid solution of palladium. The salts were characterized by a combination of physicochemical methods, and their crystal structures were determined by X-ray diffraction. The conformation of the [Pd(NO3)(4)](2-)anion was studied in detail using crystal structure data and density functional theory calculations. A combination of nonhygroscopicity and stability under normal conditions, together with thermolability, high solubility in various solvents, and the lability of nitrato ligands, makes salts 1-3 valuable starting materials for the synthesis of Pd compounds and the preparation of Pd-containing catalysts. In this work, these applications were illustrated by the synthesis of heteroleptic Pd(II) nitrato complexes with N-donor ligands and the preparation of Pd0.1Ni0.9/SiO2 catalysts, which worked well in H-2 generation from hydrazine hydrate. Generally, it was shown that up to several weight percent of Pd can be deposited on various oxide/hydroxide supports using a straightforward chemisorption procedure from acetone solutions of 1-3.