A new Cu4I4-cluster-based compound is constructed to show multifaceted photoluminescent attributes: (1) ultraviolet (UV)-excited thermo-, mechano-, and rigido-chromic phosphorescence by the OPA (one-photon absorption) pathway, due to the interchanging emissions from cluster-centered (3CC) and halide-to-ligand charge-transfer (3XLCT) excited triplet states, (2) the ability to convert X/γ-ray and near-infrared (NIR) radiation to visible-light emission, in which the heavy Cu4I4 cores serve as the efficient X/γ-PEA (photoelectric absorption) or NIR-TPA (two-photon absorption) trapper and convertor to photons in the visible spectrum from the same emissive triplet states as those produced by UV excitation. This all-in-one compound affords a highly integrated nanolab for understanding and exploiting a wide range of photophysical phenomena simultaneously and is further fabricated into fiber-coupled long-range, in situ cryogenic thermometer and poly(methyl methacrylate) (PMMA)-embedded monolith gel, providing access to advanced applications in multifunctional optical materials and devices.