Metal nanocluster composite glass prepared by 180keV Cu ions into silica with dose of 5×10 16 ions/cm 2 has been studied. The microstructural properties of the nanoclusters has been verified by optical absorption spectra and transmission electron microscopy (TEM). Third-order nonlinear optical properties of the nanoclusters were measured at 1064 and 532nm excitations using Z-scan technique. The nonlinear refraction index, nonlinear absorption coefficient, and the real and imaginary parts of the third-order nonlinear susceptibility were deduced. Results of the investigation of nonlinear refraction by the off-axis Z-scan configuration were presented and the mechanisms responsible for the nonlinear response were discussed. Third-order nonlinear susceptibility χ (3) of this kind of sample was determined to be 8.7×10 −8 esu at 532nm and 6.0×10 −8 esu at 1064nm, respectively.