Exploration of the global phase emergence behaviors in the quasi-2D HP systems reveal that various HP crystallites emerge, thus causing notable phase inhomogeneities in the film matrices. To spatially resolve and investigate the local phase inhomogeneities in the synthesized film matrices, Hyperspectral cathodoluminescence (CL) microscopy, integrated with a Scanning electron microscope (SEM), is utilized. Figure shows the surface SEM images of the quasi-2D HP films with different spacer cations. Here, a fixed 3D ratio of 60% was adopted for constructing quasi-2D HP films, which most likely offer 3D-like matrices as deduced from NMF analysis. It was found that the selection of a molecular spacer renders a distinctive surface morphology.