Chiral recognition is crucial for applications in chiral purity assessment and biomedical fields. However, achieving chiral recognition through visible room temperature phosphorescence remains challenging. Here, two chiral molecules, designated as host and guest are synthesized, which possess similar structural configurations. A viable strategy involving a chiral configuration‐dependent energy transfer process to enable selective phosphorescence expression is proposed, thereby enabling chiral recognition in a host‐guest doping system. The chiral and structural similarity between host and guest facilitates efficient Dexter energy transfer due to the reduced spatial distance between the molecules. This mechanism significantly enhances the intensity of red phosphorescence from the guest molecule, characterized by an emission peak at 612 nm and a prolonged lifetime of 32.7 ms. This work elucidates the mechanism of chiral‐dependent energy transfer, demonstrating its potential for selectively expressing phosphorescence in chiral recognition.