Although iron has been known and widely used in coordination and organometallic chemistry for decades and N-heterocyclic carbenes (NHCs) have also been used for about half a century, their combination surprisingly did not become a hot topic in chemistry until this last decade. This review presents several recent and stimulating developments in homogeneous catalysis done mainly using iron/NHC-based catalysts. Of particular interest are the roles of iron/NHC complexes in cross-coupling Kochi reactions, C?C bond formation reactions and hydrofunctionalization, and more particularly in hydrosilylation. Our review summarizes the key developments in these fields.