► We show how mid-IR emission spectra of asteroids can constrain their surface composition and structure. ► We demonstrate that a large fraction of the large main belt asteroids possess a highly porous surface. ► A new laboratory sample preparation method allows us to constrain their surface composition. Emission features in the mid-IR domain (7–25μm) are quite ubiquitous among large asteroids and therefore offer the potential to uncover their surface composition. However, when comparing these spectra with the actual laboratory spectra of both minerals and meteorites, they do not necessarily match. Here, and in a companion paper by King et al. (in preparation, 2012), we show that by modifying the sample preparation – typically by suspending meteorite and/or mineral powder (<30μm) in IR-transparent KBr (potassium bromide) powder – we are able to reproduce the spectral behavior of those main-belt asteroids with emissivity features. This resulting good match between KBr-diluted meteorite spectra and asteroid spectra suggests an important surface porosity (>90%) for the first millimeter for our asteroid sample. It therefore appears that mid-IR emission spectra of asteroids do not only carry information about their surface composition but they can also help us constraining their surface structure (under-dense versus compact surface structure), as suggested by Emery et al. (Emery, J.P., Cruikshank, D.P., van Cleve, J. 2006. Icarus 182, 496–512) in the case of the Jupiter Trojans. The large surface porosity inferred from the mid-IR spectra of certain asteroids is also implied by two other independent measurements, namely their thermal inertia and their radar albedo. We further clarified how much compositional information can be retrieved from the mid-IR range by focusing our analysis on a single object, 624 Hektor. We showed that the mid-IR range provides critical constraints (i) on its origin and of that of the red Trojans that we locate in the formation regions of the comets, and (ii) on the primordial composition of the dust present in the outer region (>10AU) of the Solar System’s protoplanetary disk. Future investigations should focus on finding the mechanism responsible for creating such high surface porosity.