In this work, a series of Ag-based catalysts with different metal aggregation levels, from Ag single atoms (Ag/WOx@Al2O3), through Ag5 metal clusters (Ag-LTA) to ~8 nm Ag metal nanoparticles (Ag/Al2O3), were systematically investigated as a function of temperature at the NOTOS beamline (ALBA-CELLS). The proven high structural stability of these materials allowed to minimize the contribution of the structural disorder to the σ2 factor, attributing the vibrational atomic disorder as the main component due to purely thermal effects. This effect was clearly observed during the progressive dampening of the |χ(R)|magnitude of FT k3-EXAFS and the increase of the σ2 on rising temperatures. Implementation of the correlated Einstein model allowed extracting information about the variations in the local vibration of the metal atoms in the different materials. The lower ϴE is, the higher the corresponding σ2 value at any temperature and, likewise, the vibrational disorder. This can also be translated to the strength of the atomic bonds, where an increase in the vibrational motion can refer to weakly bonded atoms, considering a harmonic oscillatory behaviour. These measurements will provide preliminary information for robust and reliable data analyses on catalysts with different metal aggregation degrees, down to mononuclear isolated sites, under in situ/operando conditions.