Quaternary N‐aryl‐DABCO salts were introduced for the first time as a highly selective sensing platform for thiols and selenols. By employing this platform, a highly sensitive coumarin based "off‐on" fluorescent probe was designed and synthesized. The probe possesses a good solubility in water, low background fluorescence, and, most importantly, demonstrates high selectivity to aryl thiols and selenols over their aliphatic counterparts and other common nucleophiles. A dramatic increase in fluorescent intensity is achieved through the selective cleavage of the quaternized DABCO‐ring, yielding a piperazine derivatives with a high fluorescent quantum yield (~72%). Moreover, stability of the probe to the most used reducing agents DTT and TCEP was demonstrated. Limits of detection for p‐thiocresol and phenyl selenide were evaluated to be 22 nM and 6 nM respectively.