AbstractTwo Curcumin (Cur) based mixed ligand complexes of Nickel have been investigated for their optical nonlinearity (NLO). Physicochemical characterization of two nickel precursors and their interaction with curcumin produced two molecules, namely Ni(C3S5)(Cur).2H2O (abbreviated as NiThCur) and NiCl(Cur)(PPh3) (abbreviated as NiTppCur). Additionally the Conceptual‐Density‐Functional‐Theory (CDFT) studies were performed. CDFT‐based optimization parameters of both molecules are theoretically interpreted. HOMO‐LUMO energy gap of NiThCur and NiTppCur were calculated 1.474 eV and 2.744 eV respectively. Both molecules demonstrated good NLO activities, studied by a Z‐scan approach and additionally with a Differential Four wave Mixing (DFWM) technique. Preliminarily investigations showed that the molecules can be potential optical limiters (OL). These studies divulge the exhibition of a 3‐photon absorption (3PA) mechanism by the synthesized molecules. NLO absorption 3PA coefficient (γ) value of 1.34×10−24 m3/W2, third‐order optical susceptibility (χ(3)) value of 1.543×10−11 esu, and the figure of merit 6.64×10−14 esu was observed for the NiThCur complex and γ=3.61×10−24 m3/W2, χ(3)=1.521×10−11 esu, and FoM=5.61×10−14 esu for NiTppCur with Z‐scan (γ and χ(3)) and DFWM methods, respectively. Normalized transmittance (NT) exhibited a decrease to 78.5 % from 100 % in NiThCur and to 69.5 % in NiTppCur. Optical limiting calculations are also presented.