Intermolecular amine−phenol interactions are largely recognized as unique models with diverse supramolecular interactions. However, fluorescence (FL) variations originating from such interactions are rare. Herein, FL changes are well realized from amine−phenol interactions to identify an important biomarker, biogenic amines (BAs). A simple, inexpensive, and thermally stable anthracenylphosphonate is linked with 2,2′biphenol to design a functional dual-state emitter. Among the various amines tested, this emitter displays superior sensitivity with the lowest possible limit of detection as 5.8−9.7 ppb with aliphatic polyamines such as 1,3-, 1,4-, 1,5-, and 1,6-diamines and spermidine in the solution phase. Fast, on-spot detection of the BA vapors was visually conducted through a notable high-contrast change from blue to yellow emission in the solid state. FT-IR, 1 H/ 31 P NMR, and mass spectroscopic studies identify the groundstate amine−phenol interactions. The failure in BA detection with the 2,2′-dimethoxy-biphenyl-linked analog verifies the role of amine−phenol interactions. Mechanistic studies determine amine−phenol interactions in the ground and excited states. The molecular structure and packing of the doubly twisted probe are documented with a substantial void space facilitating close contact of the BAs with the strong amine−phenol interactions desired for efficient detection. Finally, this probe governs the freshness of a piece of Catla catla fish and prawn. Further, a remarkable concentration-controlled diverse emission with a red shift difference of 141 nm is detected with 1,3-diaminopropane (1,3-DAP) vapor (from 29 to 319 mg/L) for the first time. Thus, a cost-effective device is developed to detect 1,3-DAP at a precise concentration, visible through the naked eye.