The use of lanthanide complexes as catalysts in organic synthesis is currently of intense interest. In particular, organolanthanide complexes are of rapidly growing importance, and hence the understanding of the binding behavior of f orbital as well as the ionic/covalent characteristics of lanthanocene-based complexes is of significance with respect to their reactivity and their role as catalyst in organic synthesis. The purpose of this review is to give a survey of recent progress in theoretical studies on organo-f-element complexes and to highlight successful applications of density functional and quantum chemical molecular dynamics methods.