Laser ablation (LA) in liquids has been used for the development of various nanoparticles (NPs); among them, Ag NPs in aqueous solutions (usually produced by nanosecond (ns) LA) have attracted exceptional interest due to its strong plasmonic response. In this work, we present a comprehensive study of the LA of Ag in water, chloroform and toluene, with and without PVP, using a picosecond (ps) Nd:YAG laser and we consider a wide range of LA parameters such as the laser wavelength (1064, 532, 355 nm), the pulse energy (0.3-17 mJ) and the number of pulses. In addition, we consider the use of a secondary nanosecond laser beam for the refinement of the NPs size distribution. The optical properties of the NPs were evaluated by in situ optical transmittance measurements in the UV-vis spectral ranges. The morphology of the NPs and the formation of aggregates were investigated by Scanning Electron Microscopy and High-Resolution Transmission Electron Microscopy. The ps LA process resulted in the development of bigger Ag NPs, compared to the ns LA, compatible with the size requirements of the printed organic electronics technology. The optimum conditions for the ps LA of Ag in organic solvents include the use of the 355 nm beam at low pulse energy (<1 mJ); these conditions rendered isolated Ag nanoparticles manifesting strong and well defined surface plasmon resonance peak. The use of the secondary ns laser beam was proven to be able to refine the nanoparticles to intermediate size between those produced by the single ns or ps LA. 2014 Elsevier B.V. All rights reserved.