Chromophore is a molecule or a part of a molecule which is responsible for its appearance color. This definition has been evolving over time with the progress of science. Contemporary scientific advances have expanded its meaning: to an inclusive level, chromophore is an irreducible collective of fundamental particles, which can represent the photophysical (optical physical) properties of the macroscopic matter. Previous studies have already found that the same molecule can have different photophysical properties under different condensed states. Therefore, it is straight forward to conclude that the definition of chromophore should take such extrinsic influencing interactions of this given molecule into consideration, thus simply taking the smallest unit such as a molecule is not accurate. A good example is quantum dots. Same species of quantum dots possess the identical smallest chemical unit but can emit very differently due to quantum confinement effect, thus defining the smallest unit as the chromophore is apparently fallacious. In solid polymeric compositions, the chemical unit or building blocks may differ from the spectroscopic unit depending on how these chemical units interacts within their ensemble to evolve new properties such as a new transition dipole. As thus, understanding the evolution of photophysical behaviors between the targeted unit and neighbors is of much importance to determine whether they should be considered as one chromophore or many. This requires a thorough understanding towards the evolution of photophysical properties of a collective, and the construction of such collective will need to pay extra attention to, as any structural factor could have changed some photophysical interactions of the collective. The introductory chapter discusses the material platform and fundamental photophysics investigated in this dissertation. Chromophore assembly (CA) as a sylloge of several classes of self-assembled materials, including metal-organic frameworks (MOFs), covalent-organic frameworks (COFs), porous organic polymers (POPs). Among them, MOF-based CAs (MOF-CAs) featuring with the ease of synthesis, demonstrate incomparable promises to construct such collective with several appealing characteristics, including component diversity, chemical stability, structural porosity, and post-synthetic versatility (Chapter 1.1). As for here, the main target to achieve using these assemblies is to understand the interaction between adjacent chemical monomeric units, therefore their spatial arrangements are of the paramount importance. As modern theory discovered, both ordered and random systems can be very important for novel quantum material developments. Both crystalline and amorphous arrangements of monomeric units can be achieved by adopting different classes of materials. MOF-CAs could achieve the precise control of spatial arrangement including distance, direction, and dihedral angle by its crystalline structures, whereas porous organic polymer-based CAs (POP-CAs) could feature a total randomness. Photophysics, as the research topic targeting the firsthand knowledge gained by interrogating the information provided by the propagating light after its interaction with matters, could provide crucial knowledge of the targeted matter. Hence, photophysical properties could provide fundamental understanding of the targeted matter (Chapter 1.2). State-of-the-art spectroscopic methods and instrumentation have made it possible to critically examine new structures to correlate photophysics with the chemical structure of their assemblies. By combining multiple spectroscopic techniques along with theoretical study, several correlations between the electronic properties of the matter, such as structural features, have been investigated. To illustrate, some unique topology-dependent photophysical behaviors found in chromophore assemblies are introduced (Chapter 1.3). In this dissertation, the feasibility of using specific types of MOF-CAs to conduct unique photophysical studies has been carefully chosen and verified (Chapter 2). Next, with the help of first principles computations, the nature of several electronic excited states as a function of different extent of Van der Waals or electronic interaction in MOF-CAs is unveiled, and experimentally studied with several environmental variates (Chapter 3). The knowledge was then articulated to devise a strategy to improve resonance energy transfer process in MOF-CAs. Here, low electronic symmetry of linker and directionally aligned transition dipoles of their collective ensembled are found beneficial to improve such photophysical process in a bottom-up manner (Chapter 4). Then, a series of MOFs were rationally designed to examine the feasibility and extent of a nonlinear excitonic process, singlet fission, to promote the generation of carriers usable for many applications including light-harvesting applications. The outcome demonstrated MOF-CA is a powerful tool to design such materials and is more capable in terms of its tunability (Chapter 5). At last, a set of randomly oriented CAs in POP were examined for underlying excited state dynamic process that highlights a thermal activated delayed fluorescence (TADF) involving S1 and low-lying T2 excited states (Chapter 6). This dissertation has highlighted unique yet tunable excited-state features and photophysical processes within the well-defined molecular ensemble realized via porous frameworks. These photophysical properties differ from those of their respective molecular system in their solubilized forms. Studies in this dissertation demonstrates a reliable platform to investigate multibody chromophore systems and suggested several valuable discoveries and lights the way for the study of novel chromophore assembly systems.