A series of Ru-II or Fe-II trischelate complex salts containing N-methyl/aryl-2,2':4,4' ':4',4' ''-quaterpyridinium ligands that has previously been subjected to quadratic nonlinear optical studies (Coe, B. J. et al. J. Am. Chem. Soc. 2005, 127, 13399) has now been investigated for two-photon absorbing behavior. Z-scan measurements using a 750 nm laser afford reasonably large two-photon absorption (2PA) cross-sections sigma(2) of ca. 62-180 GM for the Ru-II complexes, but only very weak 2PA is observed for the Fe-II compounds. The excited-state and 2PA properties of the representative chromophore [Ru-II(Me(2)Qpy(2+))(3)](8+) (Me(2)Qpy(2+) = N' ',N' ''-dimethyl-2,2':4,4' ':4',4' ''-quaterpyridinium) have also been investigated by using semiempirical intermediate neglect of differential overlap/multireference-determinant single and double configuration interaction computations with the optimized geometry obtained via density functional theory. The calculated sigma(2) value of ca. 624 GM at 1.70 eV for this metal-to-ligand charge-transfer chromophore is about 10 times larger than that obtained from the Z-scan studies.