The effect of various experimental parameters and the presence of chemical modifiers on the atomization kinetics of gold have been investigated. The dissipation process of the atomic vapour is also studied and the diffusion parameters calculated in the absence and in the presence of chemical modifiers. The chemical modifiers studied are ascorbic acid, rhenium, palladium and rhodium. In the absence of chemical modifiers, a two-precursor atomization mechanism is observed in distinctive different temperature regions. When a long pyrolysis step and low masses of gold are employed, an atomization from dispersed particles with low E a value is observed in the low temperature region (LT region). At high masses of gold, a fractional order atomization from gold agglomerates with high, mass-dependent, E a values, approaching the heat of vaporization, Δ H vap, is observed in the high temperature region (HT region). In the presence of ascorbic acid, a high E a value is obtained in the LT region, suggesting a fast atomization from surface particles at the active sites produced by the pyrolysis of ascorbic acid and a low E a value is obtained in the HT region, with first-order kinetics, which indicates a desorption process through the micropores of the amorphous carbon residue of ascorbic acid. In the presence of 5 μg Re, a two-precursor mechanism is also found, with a high E a value in the LT region, suggesting vaporization from small clusters, and a low E a value in the HT region with a first-order kinetics, indicating vaporization of disperse particles from the graphite surface. In the presence of 0.1–1 μg Pd, a two-precursor mechanism is also observed. The first process, in the LT region, has a low E a value, which indicates vaporization of disperse particles from the available free active sites of the graphite surface. The second process, in the HT region, begins at the appearance temperature of Pd and shows a high E a value and first-order kinetics, which means that release of gold atoms occurs only after the vaporization of Pd has begun. In the presence of Rh, a mass-dependent E a value is found in the LT region, suggesting atomization from gold clusters. However, in the HT region, the generation of atomic vapour of Au is kinetically controlled by the release of the Rh modifier.