The biological luminescent metal-organic framework (bio-LMOF), (Me 2 NH 2 ) 2 Zn 6 O(Ade) 4 (TCPPE) 2 ( 1 ) {H 4 TCPPE = tetrakis4-(4-carboxyphenyl)phenylethene, Ade = adenine} was successfully designed and synthesized under hydrothermal conditions, with two channels of different sizes. The absolute fluorescence quantum yields of complex 1 and activated 1 are up to 77.6% and 85.9%, respectively. Activated 1 exhibits outstanding water stability and excellent selective luminescence sensing for amino acids and monosaccharides. The fluorescence quenching efficiencies of activated 1 towards l -Nph and d -Nga are 86.35% and 91.60%, respectively. Besides, activated 1 also displays highly quenching responses to l -Nph and d -Nga at fairly low concentrations, and the limits of detection for l -Nph and d -Nga are estimated to be 0.149 ppm and 1.612 ppm, respectively. Meanwhile, in multiple cycling experiments, activated 1 still has excellent cycling stability. These phenomena indicate that activated 1 can be utilized as a fast responsive biological luminescent sensor, which is a rare example for bio-LMOFs. A tetraphenylethene-based biological luminescent metal-organic framework with high fluorescence quantum yield is developed for selective and sensitive detection of amino acids and monosaccharides in aqueous medium.