The magnetic relaxation and anisotropy of 3- and 4-coordinate lanthanide complexes were systematically investigated, and the change of SMM behavior originating from the equatorially coordinating ligand field was successfully elucidated through combined experimental and theoretical studies. Remarkably, a novel approach taking into account the different contributions of atomic charges, dipole moments, and quadrupole moments was used to map the electrostatic potential around the metal center in the Dy(III) derivatives, revealing the key role played by the ligands as a whole and not just by the coordinating donor atoms as often considered