The phase behavior of supramolecular nanocomposite thin films was systematically investigated as a function of nanoparticle (NP) loading from 1 to >50 wt %. The coassembly of NP and supramolecule can be divided into five regimes, from a supramolecule-guided assembly to a NP governing assembly process, depending on the energetic contributions from the surface energy, NP-supramolecule interaction; and the kinetic pathway of the assembly process. A range of morphologies such as 1D NP chains, 2D sheets, 3D NP assemblies, and NP solids can be readily obtained, providing opportunities to meet structural control in nanocomposites for a wide range of applications.