• Effect of polar-polar miscible liquids on ablation. • Effect of polar-nonpolar immiscible liquids on ablation. • Influence of liquid parameters on silver nanoparticles and nanostructures. In this article we report the results obtained from ultrafast laser ablation of silver targets immersed in polar/polar miscible and polar/non-polar immiscible combinations of liquids with laser pulses of ∼2 ps duration. Former combination included acetone and water while the latter combination was toluene and water. The prepared silver nanoparticles in pure acetone, pure water (double distilled) were compared with the silver nanoparticles fabricated in acetone–water (double distilled) mixture. Similarly, synthesized silver nanoparticles in pure toluene, pure water were compared with the silver nanoparticles fabricated in toluene-water mixture. The TEM images of Ag NPs generated in acetone demonstrated that average size of Ag nanoparticles fabricated in acetone, water, and double distilled water–acetone mixture were ∼4.5 ± 1.8 nm, ∼16 ± 4 nm, and 5 ± 1.7 nm, respectively. In the case of double distilled water-toluene combination, formed silver nanoparticles were trapped inside the graphitic matrix. Obtained morphologies and average sizes of silver nanoparticles in polar/polar miscible and polar/non-polar immiscible combinations demonstrated the effect of the difference in the formatted cavitation bubble (CB). In general, products of ablation are determined by the dynamics of CB and its oscillations those depend on the intrinsic behaviour of aqueous medium of interest.