Despite increasing evidence that plant diversity in experimental systems may enhance ecosystem productivity, the mechanisms causing this overyielding remain debated. Here, we review studies of overyielding observed in agricultural intercropping systems, and show that a potentially important mechanism underlying such facilitation is the ability of some crop species to chemically mobilize otherwise-unavailable forms of one or more limiting soil nutrients such as phosphorus (P) and micronutrients (iron (Fe), zinc (Zn) and manganese (Mn)). Phosphorus-mobilizing crop species improve P nutrition for themselves and neighboring non-P-mobilizing species by releasing acid phosphatases, protons and/or carboxylates into the rhizosphere which increases the concentration of soluble inorganic P in soil. Similarly, on calcareous soils with a very low availability of Fe and Zn, Fe- and Zn-mobilizing species, such as graminaceous monocotyledonous and cluster-rooted species, benefit themselves, and also reduce Fe or Zn deficiency in neighboring species, by releasing chelating substances. Based on this review, we hypothesize that mobilization-based facilitative interactions may be an unsuspected, but potentially important mechanism enhancing productivity in both natural ecosystems and biodiversity experiments. We discuss cases in which nutrient mobilization might be occurring in natural ecosystems, and suggest that the nutrient mobilization hypothesis merits formal testing in natural ecosystems.