CaCu3Ti4O12 (CCTO) thin films were successfully prepared on LaAlO3 substrates by pulsed laser deposition technique. We measured the nonlinear optical susceptibility of the thin films using Z-scan method at a wavelength of 532 nm with pulse durations of 25 ps and 7 ns. The large values of the third-order nonlinear optical susceptibility, χ (3), of the CCTO film were obtained to be 2.79×10−8 esu and 3.30×10−6 esu in picosecond and nanosecond time regimes, respectively, which are among the best results of some representative nonlinear optical materials. The origin of optical nonlinearity of CCTO films was discussed. The results indicate that the CCTO films on LaAlO3 substrates are promising candidate materials for applications in nonlinear optical devices.