The magnificent electronic, magnetic, and spectroscopic properties of trivalent lanthanide ions leading to their industrial and analytical applications have resulted in the emerging interest in the study of the coordination of their complexes. Many such compounds containing multidentate chelators have been reported for their implementation in magnetic resonance imaging (MRI), luminescent sensors, catalytic systems, etc. The present work describes the chelation and bonding of a hydroxypyranone-based hexadentate chelator, (tris[(5-hydroxy-4-oxo-pyran-2-yl)methyl]benzene-1,3,5-tricarboxylate), TBHPY, toward some trivalent lanthanide ions, viz. La(III), Eu(III), Gd(III), Tb(III), and Lu(III). The geometry of these lanthanide complexes was obtained using quantum mechanical methods by satisfying the coordination number using water molecules. The geometry, bonding, and electronic properties of all the complexes as computed using quantum mechanical computational tools are discussed in detail to provide a broad understanding of these coordination polyhedra.