In this paper, a series of organic compounds (L1-L6) with a D-pi-A conjugation system were prepared. The investigations of third-order nonlinear optical (NLO) properties indicate that L1-L6 show different degrees of third-order NLO responses. It is surprising that introducing metal ions can effectively regulate their third-order NLO properties and even change the type of nonlinear absorption signal from reverse saturable absorption to saturable absorption, which can be attributed to the formation of coordination bonds between metal ions and L1-L6. It has aroused our tremendous interests in regulating third-order NLO performance. The regulation mechanisms were also discussed through the pump probe measurements and the density functional theory. The enhancement of electron transfer efficiency is considered to be the key to improving NLO performance. Furthermore, we also obtained two coordination complexes [Cu(L1)(2)(NO3)(2)] (1) and [Cd(L1)(2)I-2] (2) based on L1, which further proved the coordination between metal ions and L1-L6. Ligand-to-metal or metal-to-ligand charge transfer makes more electronic delocalization, leading to better third-order NLO properties. This work provides new ideas and explorations for the excogitation of third-order NLO materials.