Nonlinear optical characterizations were performed on monodispersed silver (Ag) nanoparticles (NPs) of various sizes using a picosecond Z-scan technique with excitation wavelengths of 532 nm and 1064 nm. The Ag NPs were fabricated using a heterogeneous condensation technique in a gas medium. The nonlinear refraction values were higher for the monodispersed Ag NPs whose surface plasmon resonance (SPR) peak is closer to the excitation wavelength. The higher nonlinear optical response is explained in terms of an electric field enhancement near the SPR. Moreover, the fabrication method allows the tailoring of the nonlinear refraction index of the Ag NPs by tuning the SPR peak of the sample. A comparison of the nonlinear refraction index of the monodispersed and polydispersed Ag NPs showed that the nonlinear refractive index of the monodispersed Ag NPs is higher.