Ultra-thin CoPt3 nanoparticle films have been prepared on SiO2 surfaces using a Langmuir-Blodgett (LB) deposition technique. The structural properties of the overlayers have been investigated by grazing-incidence small-angle x-ray scattering (GISAXS) and high-resolution scanning electron microscopy (SEM) for the first time. Self-assembly of the nanoparticles is found and with GISAXS an average particle-particle distance of (8.23 ± 0.06) nm is determined, in good agreement with the SEM results. A particle correlation length of (22.3 ± 1.2) nm was derived which is shown to be independent of the surface coverage. The latter quantity may be controlled by choice of a suitable retraction speed during the LB step.