Two new palladium complexes [Pd(MEA)2Cl2] (1) and [Pd(MEA)2Br2] (2) [MEA = (2-methoxyethyl)amine] were synthesized by the reaction of 2 equiv. of MEA with PdCl2 or [(cod)PdBr2] (cod = cycloocta-1,5-diene), respectively. Single-crystal X-ray diffraction analysis of 1 and 2 revealed the formation of square-planar trans complexes with palladium coordinated by chloride/bromide ions and N-atoms of MEA bonded in a monodentate fashion. Given their molecular form and solubility, 1 and 2 act as intractable precursors to Pd nanoparticles by microwave-assisted synthesis. The influence of the reaction temperature, irradiation time and surfactant (PVP) concentration on the size (5–40 nm) of the resulting particles was studied by DLS (hydrodynamic diameter) and TEM analyses (particle size). The growth mechanism of the nanoparticles depended on the type of halide ligand. Powder X-ray diffractometry confirmed the formation of elemental Pd particles that were embedded in carbonized wood to examine their potential as a catalyst. The catalytic activity of these nanoscale particles was evaluated in carbon–carbon cross-coupling reactions by using Heck, Suzuki and Sonogashira reactions as benchmark models. The investigations included recycling experiments that resulted in total turnover numbers of 4321 (Heck), 6173 (Sonogashira) and 8223 (Suzuki).