Spin-coating electrostatic self-assembly (SCESA) is utilized to fabricate a single layer of carboxylic-acid-coated Pd nanoparticles (NPs) (D??5 nm) on an oppositely charged surface. The packing density of a NP monolayer formed on a rotating solid substrate (3000 rpm) was examined with regards to various parameters, including the particle concentration, the pH, and the ionic strength of the solution. Initially, the packing density grew exponentially with increases in the particle concentration, up to a maximum value (of 8.4 ´ 1011/cm2) at 1.2 wt%. The packing density was also found to increase drastically as the pH decreased and the ionic strength of the solution increased; these trends can be attributed to a reduction in the interparticle repulsions among the NPs in the solution and on the substrate. The best result of this study was achieved in a 1.2 wt% solution at pH 8; under these conditions, an NP monolayer with the highest density (namely, 1.6 ´ 1012/cm2) was obtained.