This work presents a systematic study of the significant role of the surface physicochemical alterations produced during the laser ablation of massive iron disks submerged in different solvents on the generation of colloidal iron nanoparticles. For that purpose, the laser ablation thresholds and the incubation coefficients for various pulse numbers per site and pulse energies have been measured under distilled water (DW) and ethanol (EtOH). After that, a complete physicochemical characterization of these targets indicated higher threshold fluence values for the ablation experiments conducted in EtOH than those performed in DW. The threshold fluence values decreased also with the decrease of the pulse overlap for both solvents, being it much more pronounced in EtOH. In addition, the related incubation coefficient showed that the incubation effect is lower for experiments conducted in DW. The characteristics of the synthesized nZVI particles were also a function of the solvent nature and the pulse overlap: laser ablation in DW leaded to iron oxide nanoparticles, whereas core-shell iron nanoparticles were obtained in EtOH. Moreover, high pulse overlap values lead to chemical alterations, resulting in a decrease of the composition homogeneity and a strong increase of the nanoparticle polydispersity.