This research reports the preparation and characterization of copper nanoparticles modified by didecyl benzene sulfonate (DBS). The Cu nanoparticles’ size was determined to be 4.0 nm by transmission electron microscope (TEM). The X-ray photoelectron spectrometry (XPS) results show that there are interactions between the copper nanoparticles and DBS function group. The nonlinear optical properties were studied by the four-wave mixing method. The value of χ(3)/α0 was found to be 6.9×10-11 esu cm.