Functional ligand-protected metal cluster nanomaterials with increased two-photon absorption and two-photon excited emission might result in new technologies within the fields of bio-imaging applications. During this article, I review the two-photon absorption/emission properties of atomically precise ligand-protected silver and gold nanoclusters, coined “ligand-core” NLO-phores. This includes quantum-chemical methodologies using time-dependent density theory. I will analyze physical phenomena and trends resulting in giant two-photon absorption/emission responses of a number of series of model nanoclusters. I will then focus my review on the effects of the relaxation pathways within the linear and nonlinear optical regime, similarly as innovative ways aiming at enhancing their two-photon emission responses.