Abstract The fate of Mercury’s exospheric volatiles and, in a lesser way, of the refractory particles absorbed in the first few centimeters of the surface both depend highly on the temperature profile with depth and its diurnal variation. In this paper, we review several mechanisms by which the surface temperature might control the surface/exosphere interface. The day/night cycle of the surface temperature and its orbital variation, the temperature in the permanent shadow regions, and the subsurface temperature profiles are key thermal properties that control the fate of the exospheric volatiles through the volatile ejection mechanisms, the thermal accommodation, and the subsurface diffusion. Such properties depend on the solar illumination from large to small scales but also on the regolith structure. The regolith is also space-weathered by the thermal forcing and by the thermal-mechanical processing. Its composition is changed by the thermal conditions. We conclude by discussing key characteristics that need to be investigated theoretically and/or in the laboratory: the dependency of the surface spectra with respect to temperature, the typical diffusion timescale of the volatile species, and the thermal dependency of their ejection mechanisms.