In a Langmuir trough, successive compression cycles can drive a two-dimensional (2D) nanoparticle supracrystal (NPSC) closer to its equilibrium structure. Here, we show a series of equilibrated 2D NPSCs consisting of gold NPs of uniform size, varying solely in the length of their alkanethiol ligands. The ordering of the NPSC is governed by the ligand length, thus providing a model system to investigate the nature of 2D melting in a system of NPs. As the ligand length increases the supracrystal transitions from a crystalline to a liquid-like phase with evidence of a hexatic phase at an intermediate ligand length. The phase change is interpreted as an entropy-driven phenomenon associated with steric constraints between ligand shells. The density of topological defects scales with ligand length, suggesting an equivalence between ligand length and temperature in terms of melting behavior. On the basis of this equivalence, the experimental evidence indicates a two-stage 2D melting of NPSCs.