The thermal stability of catalytic precursors is of major importance for the synthesis of single-walled carbon nanotubes (SWNTs) with narrow diameter distributions by chemical vapor deposition at high temperature. We report a study of the thermal stability of iron (Fe) and iron oxide (Fe2O3) nanoparticles with narrow size distribution grown onto Si/SiO2 hydroxylated flat substrates. Whereas the Fe2O3 nanoparticles are thermally stable up to 900 °C, above their reducing temperature of ∼700 °C, the size distribution of Fe nanoparticles increases and broadens. An accurate analysis of atomic force microscopy data shows that this instability is due to a diffusion−coalescence mechanism, ruling out a possible Ostwald's ripening mechanism. The origin of this behavior is attributed to the dewetting of the nanoparticles. Using the thermally stable oxide nanoparticles as catalytic precursors, SWNTs can be successfully grown using a methane−hydrogen mixed gas. Statistical analysis of the SWNTs Raman radial breathing modesmeasured using four excitation wavelengths indicates that the diameter distribution of the nanotubes is centered at 1.3 ± 0.03 nm with a narrow full width at half-maximum of 0.3 ± 0.05 nm. The analysis of our results compared with other results recently published suggests that the metal−surface interaction could play a key role in the catalytic decomposition of methane and in the growth of SWNTs.