A new coumarin diester has been isolated from Polygala paniculata L. (Polygalaceae) by a combination of flash chromatography on silica gel and preparative reversed‐phase chromatography. Its structure has been determined as 3′‐O‐acetyl‐4′‐O‐benzoylkhellactone (= 9‐acetoxy‐9,10‐dihydro‐8,8‐dimethyl‐2‐oxo‐2 H,8H‐benzo[1,2‐b:3,4‐b′]dipyranh‐10‐yl benzoate) by spectroscopic methods (UV, IR, 1H‐NMR, EI‐and CI‐MS) and by X‐ray analysis.