If the material is already in the active sample slot, the eyedropper has no effect.
If the eyedropper cursor is over an editable mesh or polymesh with faces selected at the sub-object level, and the mesh has a Multi/Sub-Object material applied to it, then the eyedropper picks up the sub-material. However, if the selected faces have more than one sub-material assigned to them, then the eyedropper picks up the entire Multi/Sub-Object material.