Supramolecular macrocyclic hosts have long been used in smart materials. However, their triplet emission and regulation at crystal level is rarely studied. Herein, ultralong and universal room‐temperature phosphorescence (RTP) is reported for traditional crown ethers. A supramolecular strategy involving chain length adjustment and morphological locking through complexation with K+ was explored as a general method to tune the phosphorescence lifetime in the solid state. A maximum 10‐fold increase of lifetime after complex formation accompanied with by invisible to visible phosphorescence was achieved. A deep encryption based on this activated RTP strategy was also facilely fabricated. This work thus opens a new world for supramolecular macrocycles and their intrinsic guest responsiveness offers a new avenue for versatile smart luminescent materials. Traditional crown ether is injected with fresh blood of room‐temperature phosphorescence in crystalline state. Supramolecular interactions introduced by multiple oxygen atoms and K+ were explored as a general method to tune lifetime. This work opens a new world for crown ether and its intrinsic guest responsiveness offers a new avenue for versatile smart luminescent materials.