The taste sensing capabilities of a “biomimetic tongue” based on the photoluminescence (PL) responses of metal–organic frameworks (MOFs), [In(OH)(bdc)] n (bdc=1,4-benzenedicarboxylate), [Tb(btc)] n (MOF-76, btc=benzene-1,3,5-tricarboxylate), and [Ca 3 (btc) 2 (DMF) 2 (H 2 O) 2 ]·3H 2 O are proven on aqueous solutions of five basic tastants: sucrose (sweet), caffeine (bitter), citric acid (sour), sodium chloride (salty) and monosodium glutamate (umami). For [In(OH)(bdc)] n , the tastant interacts stereochemically with poly(acrylic acid) (PAA) and alters its conformations. The frequency and magnitude of chelation between COO − pendant groups of PAA and In 3+ nodes of [In(OH)(bdc)] n framework influence the corresponding PL reponses. For MOF-76, the tastant interacts with incorporated water in MOF-76 through hydrogen bonding. The limitation of O–H bond stretching of water results in the enhancement of the PL intensity. For [Ca 3 (BTC) 2 (DMF) 2 (H 2 O) 2 ]·3H 2 O, it is added as a third MOF component to increase the precision on taste discrimination. The significance of MOF-based “biomimetic tongue” includes: (1) PAA on [In(OH)(bdc)] n mimics the taste receptor cells (TRCs) for their structural flexibility, (2) the Weber-Fechner law of human sensing that sensation is proportional to the logarithm of the stimulus intensity is observed between the PL emission response of MOF-76 and the concentration of tastant, (3) the strength of taste is quantified by the τ scale and the PL emission intensity of MOF-76, which are dependent on the logarithmic tastant concentration, (4) the tastant is identified by the shape of the 3D principal component analysis contour map (i.e., pattern recognition method), and (5) the fabrication of [In(OH)(bdc)] n /PAA film by brushing is illustrated.