A comparative study of vacuum versus ambient pressure inert gas thermogravimetry was performed on silver carboxylates compounds. Some of the complexes from this group have been previously successfully applied as precursors for both chemical vapour deposition and electron beam-induced deposition. Considerable differences were found between the thermogravimetry methods, which we associate with changes in evaporation dynamics. Vacuum thermogravimetry sublimation onsets consistently occurred at lower temperatures than ambient pressure N₂-flow thermogravimetry, where the differences reached up to 120 °C. Furthermore, compound sublimation during N₂-TGA was suppressed to such an extent that significant thermal decomposition of the compounds into metal and volatile organic fragments was observed while at vacuum the same complexes sublimed as intact molecules. Moreover, thermal stability of silver complexes was investigated using isothermal thermogravimetry. These findings are interesting for the field of thin film synthesis and nanomanufacturing via chemical vapour deposition, atomic layer deposition and focused electron beam induced deposition. In all three methods, delivery of functional precursor over the substrate is crucial. The presented results prove that vacuum thermogravimetry can be used as fast method of pre-screening for novel, especially low-volatility precursors.