In this study we use ab initio calculations and a pure silicon tip to study the tip-surface interaction with four characteristic insulating surfaces: (i) the narrow gap TiO2 (110) surface, (ii) the classic oxide MgO (001) surface, (iii) the ionic solid CaCO3 (101¯4) surface with molecular anion, and (iv) the wide gap CaF2 (111) surface. Generally we find that the tip-surface interaction strongly depends on the surface electronic structure due to the dominance of covalent bond formation with the silicon tip. However, we also find that in every case the strongest interaction is with the highest anion of the surface. This result suggests that, if the original silicon tip can be carefully controlled, it should be possible to immediately identify the species seen as bright in images of insulating surfaces. In order to provide a more complete picture we also compare these results to those for contaminated tips and suggest how applied voltage could also be used to probe chemical identity.