Water‐soluble smart materials with multi‐stimuli‐responsiveness and ultra‐long room‐temperature phosphorescence (RTP) have garnered broad attention. Herein, a water‐soluble terpyridine zinc complex (MeO‐Tpy‐Zn‐OAc), featuring a simple donor‐π‐acceptor (D‐π‐A) structure is presented, which responds to a variety of stimuli, including changes in solvents, pH, temperature, and the addition of amino acids. Notably, MeO‐Tpy‐Zn‐OAc functions as a fluorescence probe, capable of visually and selectively discriminating aspartate or histidine among other common amino acids in water. Additionally, when incorporated into polyvinyl alcohol (PVA) to form the composite MeO‐Tpy‐Zn‐OAc@PVA, the material exhibits reversible writing, photochromism, and a prolonged RTP with a 14 s afterglow. These unique properties enable the composite to be utilized in potential applications such as secure data encryption and inkless printing.