Having three equatorial phenolates and one axial amine, triphenolamines are useful tetradentate ligands with unique trigonal bipyramidal geometry, in particular for early transition metals. Over the past decades, various triphenolamine ligands with different electronic and steric properties, and their transition metal complexes have been reported, including asymmetric and chiral variants. Early transition metal complexes with triphenolamines have found numerous applications in the field of organic catalysis and polymerization as notable examples. This review summarizes the recent advances in this field, mainly focusing on the synthesis and application of the early transition metal complexes with triphenolamine ligands.