<p>Solid-state (SS) luminescent materials are an important class of materials in a myriad of technological applications including light-emitting devices (LEDs) and displays, SS lasers, sensors, imaging agents, etc. Unfortunately, the design of efficient SS emitters is often plagued by sensitivity to environment/matrix (e.g. aggregation-induced quenching, AIQ), competing non-radiative relaxation pathways, and complicated emission mechanisms that are difficult to systematically study and tune. Copper-based systems have been proven to be good candidates for SS emissive materials due to their low-cost, high synthetic variation and well-defined features. Examples of copper-cluster systems, specifically, have been shown to be highly stable, exhibit high photoluminescent quantum yields (ΦPL), and are often relatively insensitive to environmental changes. However, many of these systems are complicated in nature, and often evoke additional relaxation pathways. To mitigate these issues, tetranuclear Cu(I)-pyrazolate complexes have been made which exhibit high ΦPL, matrix insensitivity and proceed through one major radiative emission pathway: cluster-centered based phosphorescence (3CC). The pyrazoles are highly tunable, and by increasing the size of the ligand substituents (H, F, Cl/Me/Br), a rigidochromic effect is observed, causing a significant blue-shift in their photoluminescence, making these viable materials for organic LEDs (OLEDs), especially in the deep-blue region. Furthermore, by increasing the chain length of the ligand substituent (e.g., Me → Et), another material which exhibits stimuli-responsive luminochromism in response to solvent vapor or heat can be achieved. This material exhibits blue ↔ green rigidochromic luminescence in response to stimuli via isomerization of the ethyl units from exo ↔ endo resulting in additional steric effects that effectively prevent rigidification of the Cu4 cluster. This additional phenomenon opens the door for further exploration of Cu(I)-pyrazolate complexes for stimuli-responsive luminescent materials (SRLMs) applications.</p>