Our work presents, for the first time, a comprehensive study of the synthesis of fully metallic platinum nanoparticles (Pt-NPs) involving the ablation process in double distilled water using a KrF excimer laser. To obtain detailed information on Pt-NP morphology and optical properties, prepared colloids were characterized using High Resolution Scanning Transmission Electron Microscopy (HR-STEM) with advanced capabilities for Energy Dispersive X-ray Analysis (EDX), UV/Vis optical spectroscopy, and Direct Analysis in Real Time—Mass Spectrometry (DART-MS). The influence of the applied laser fluence and laser repetition rate (RR) values on the characteristics of the obtained Pt-NPs and the ablation process, respectively, were also analyzed. Spherical and spherical-like nanoparticles exhibiting aggregation were produced. The Pt-NP mean size values were between 2.2 ± 1.2 nm and 4.0 ± 1.0 nm, while their interplanar distance measurements showed a face-centered cubic (FFC) Pt lattice (111), as revealed by HR–STEM measurements, for all investigated samples. The smallest mean size of 2.2 nm of the Pt-NPs was obtained using a 2.3 J cm⁻² laser fluence at a 10 Hz RR, and the narrowest size distribution of the NPs was obtained with a 2.3 J cm⁻² laser fluence at a 40 Hz RR. A linear dependence of the Pt-NP diameters versus the laser repetition rate was found at a constant fluence of 2.3 J cm⁻². The proposed eco-friendly synthesis route of Pt-NPs, because of its relative simplicity, has the potential for use in industrial production.