Luminescent metal-organic frameworks (MOFs) are widely exploited as sensors due to their versatility and sensitivity to external stimuli. Although there are numerous luminescent MOF-based thermometers or humidity sensors, only a few examples allow efficient detection of both these parameters. We present a family of MOF-materials based on or ions, 4,4′-bipyridine-N,N’-dioxide (4,4′-bpdo) linkers, and species, described by the formulas {[][]}[]∙n(solvent) ( (1), (2)) and {[][][]}∙n(solvent) ( (3), (4)). Among them, the air-stable phase of 1 (1a), deserves main recognition due to reversible water vapor sorption properties, proton conductivity, and dual photoluminescence (PL). This cationic MOF is constructed of blue-emissive 4,4′-bpdo linkers while the encapsulated hexacyanidochromate ions exhibit near-infrared PL ≈800 nm. 1a is a great platform for luminescent sensing of relative humidity (RH) and temperature utilizing the ratiometric approach based on the intensities of dual PL or the NIR-emission lifetime. The optical thermometry of high performance can be separated from the influence of RH by using the fully dehydrated phase, 1deh, stable at 0% RH. Given that, the obtained MOF encapsulating purely inorganic molecular rubies is a unique example of a multifunctional proton-conductive luminescent ratiometric sensor of humidity and temperature.