The behavior of mixed-ligand-coated gold nanoparticles at a liquid-liquid interface during compression has been investigated. The system was characterized by measuring pressure-area isotherms and by simultaneously performing in situ X-ray studies. Additionally, Monte Carlo (MC) simulations were carried out in order to interpret the experimental findings. With this dual approach it was possible to characterize and identify the different stages of compression and understand what happens microscopically: first, a compression purely in-plane, and, second, the formation of a second layer when the in-plane pressure pushes the particles out of the plane. The first stage is accompanied by the emergence of an in-plane correlation peak in the scattering signal and a strong increase of the pressure in the isotherm. The second stage is characterized by the weakening of the correlation peak and a slower increase in pressure.