The formation of Pd nanoparticles (NPs) by matrix-assisted pulsed laser evaporation (MAPLE) of a palladium acetate solution has been studied as a function of the carrier solvent, laser-pulse number, metal precursor concentration and post-deposition thermal heating. Structural and compositional analyses demonstrate that: (i) the conventional MAPLE process can induce self-reduction of the metal salt precursor, thereby leading to the formation of metallic Pd(0) NPs; (ii) the solvent critically determines the size, morphology, and size distribution of the resulting NPs; and (iii) the cumulative effects of laser-pulse number and solute concentration are less influential than the type of solvent used. For diethyl ether-derived samples, a bimodal distribution of NP sizes spanning from ∼1 nm up to 20 nm was obtained. Conversely, by using acetone, a mono-modal distribution of sizes in the ∼1 nm–6 nm range (mean diameter …