A crucial challenge to fully exploit the quasi-2D HPs to optoelectronic applications lies in the concurrent emergence of multiple quasi-2D HP phases and their spatial distributions in the synthesized film matrices. Primarily, this is caused by adopting the nonequilibrium fabrication processing, though it is optimally compatible with manifesting a fairly homogeneous 3D HP matrix . But more importantly, profound chemical interactions among the spacer cations, inorganic building blocks, and even solvents can manifest different crystallization dynamics and/or energetic pathways for each phase . Thus, a comprehensive understanding of the supramolecular interaction is vital for resolving such phase complexities in quasi-2D HPs, thereby realizing bespoke manipulation and subsequent utilization of the complex materials for optoelectronic applications.