By developing a new method for synthesizing atomically monodisperse Au15 nanoclusters stabilized with glutathione molecules and using the current state-of-the-art methods for synthesizing monodisperse protected Au25 nanoclusters, we investigated their nonlinear optical (NLO) properties after two-photon absorption. The two-photon emission spectra and the first hyperpolarizabilities of these particles were obtained using, in particular, a hyper-Rayleigh scattering technique. The influence on NLO of the excitation wavelength, the size as well as the nature of the ligands is also explored and discussed. Au15, the smallest stable thiolated gold nanocluster, presents remarkable nonlinear properties with respect to two-photon processes. The two-photon absorption cross-section at 780 nm for Au15 is ∼65,700 GM. This experimental cross-section value points to a quantum yield for two-photon emission of about 3 × 10(-7) at 475 nm for Au15. The first hyperpolarizability β for Au15 clusters (509 × 10(-30) esu), as compared to Au25 clusters (128 × 10(-30) esu), is larger considering the difference in the number of gold atoms. Also, 10(30) β per atom values reported for Au15 and Au25 clusters are more than two orders of magnitude larger than the values reported for Au NPs in the size range 10-50 nm, outlining the quantum cluster regime.