Lanthanide complex‐based luminescence thermometry and single‐molecule magnetism are two effervescent research fields, owing to the great promise they hold from an application standpoint. The high thermal sensitivity achievable, their contactless nature, along with sub‐micrometric spatial resolution make these luminescent thermometers appealing for accurate temperature probing in miniaturized electronics. To that end, single‐molecule magnets (SMMs) are expected to revolutionize the field of spintronics, thanks to the improvements made in terms of their working temperature – now surpassing that of liquid nitrogen – and manipulation of their spin state. Hence, the combination of such opto‐magnetic properties in a single molecule is desirable in the aim of overcoming, among others, addressability issues. Yet, improvements have to be made through design strategies for the realization of the aforementioned goal. Moving forward from these considerations, we present a thorough investigation of the effect that changes in the ligand scaffold of a family of terbium complexes have on their performance as luminescent thermometers and SMMs. In particular, an increased number of electron withdrawing groups yields modifications of the metal coordination environment and a lowering of the triplet state of the ligands. These effects are tightly intertwined, thus, resulting in concomitant variations of the SMM and the luminescence thermometry behaviour of the complexes.