We investigated the third-order nonlinear optical (NLO) properties of the silver (Ag) nanoparticles (NPs) of various sizes, which were produced by disintegration of commercially available 20 and 100 nm NPs in different solvents. It is observed that NPs with the sizes less or greater than 30 nm possess saturable absorption or reverse saturable absorption (or two-photon absorption), respectively. The NPs suspensions show a self-focusing effect. In addition, the third harmonic generation from the plasma plumes produced by nanosecond laser ablation of bulk Ag and Ag NPs of 100 nm and 20 nm sizes is reported. The third harmonic efficiency from the plasmas containing NPs was higher compared with the plasmas produced on the bulk silver. Finally, the ionization probabilities of Ag atom and Ag+ were calculated.