Nanoparticle (NP) superlattices are periodic arrays of nanoscale building blocks. Because of the collective effect between functional NPs, NP superlattices can exhibit exciting new properties that are distinct from those of individual NPs or corresponding bulk materials. In particular, two-dimensional (2D) NP superlattices have attracted increasing attention due to their emerging applications in micro/opto-electronics, catalysis, sensing, and other fields. Among various preparation methods, evaporation-induced interfacial self-assembly has become the most popular method for preparing 2D NP superlattices because it is a simple, low-cost, and scalable process that can be widely applied to various NPs. Introducing soft ligands, such as polymers, can not only provide convenience in controlling the self-assembly process and tuning superlattice structures but also improve the properties of 2D NP superlattices. This feature article focuses on the methods of evaporation-induced self-assembly of polymer-grafted Au NPs into free-standing 2D NP superlattice films at air/liquid interfaces and 2D NP superlattice coatings on substrates, followed by studies on in situ tracking of the self-assembly evolution process through small-angle X-ray scattering. Their application in nano-floating gate memory devices is also included. Finally, the challenges and perspectives of this direction are discussed.