This review aims to describe some recent trends in organometallic complexes containing scorpionate ligands. Particular attention will be paid to the ligands structure, reagents, and methods developed during the past decade and contextualize them within the broad field of organometallic chemistry. In fact, novel ligand design has itself become a fundamental part of most organometallic researches and many catalytic conversions have been attained by subtle modification of the metal environment through a careful choice of the ancillary ligands. This review, which is necessarily limited in scope, reports the organometallic complexes with azolylborate and azolylalkane ligands from 2008 until today and it is organized according to the metal center.