Silver (Ag) nanoparticles were successfully prepared by using the in-liquid pulsed plasma technique. This method is based on a low voltage, pulsed spark discharge in a dielectric liquid. We explore the effect of the protecting ligands, specifically Cetyl Trimethylammonium Bromide (CTAB), Polyvinylpyrrolidone (PVP), and Sodium n-Dodecyl Sulphate (SDS), used as surfactant materials to prevent nanoparticle aggregation. The X-Ray Diffraction (XRD) patterns of the samples confirm the face-centered cubic crystalline structure of Ag nanoparticles with the presence of Ag2O skin. Scanning Transmission Electron Microscopy (STEM) reveals that spherically shaped Ag nanoparticles with a diameter of 2.2 ± 0.8 nm were synthesised in aqueous solution with PVP surfactant. Similarly, silver nanoparticles with a peak diameter of 1.9 ± 0.4 nm were obtained with SDS surfactant. A broad size distribution was found in the case of CTAB surfactant.