We report the synthesis and characterization of new palladium(II) β-ketoesterate complexes [Pd(CH₃COCHCO₂R)₂] with alkyl substituents R = ^tBu, ⁱPr, Et. These compounds can have potential use in focused electron beam induced deposition (FEBID), which is a direct write method for the growth of structures at the nanoscale. However, it is still a major challenge to obtain deposits with a high metal content, and new precursor molecules are needed to overcome this. Single crystal X-ray diffraction, infrared spectroscopy, nuclear magnetic resonance spectroscopy, and density-functional theory calculations were used to confirm the compounds’ composition and structure. Using thermal analysis and sublimation experiments, we investigate their thermal stability and volatility. These studies show that the palladium complexes sublimate over the range 348–353 K under 10⁻² mbar pressure. The electron-induced decomposition of the complex molecules in the gas phase and their thin layers on silicon substrates were analysed using electron impact mass spectrometry (EI MS) and microscopy studies (SEM/EDX). They confirm that the precursor electron-induced fragmentation depends on the molecular structure. The obtained results reveal that [Pd(CH₃COCHCO₂^tBu)₂] with cis-positioned tert-butyl groups may be a promising FEBID precursor, and we carried out preliminary deposition experiments using this compound.