Two dihydroisocoumarin glucosides have been isolated from the stem bark of Caryocar glabrum (Aubl.) Pers. Their structures and absolute stereochemistry were established on the basis of extensive 1D and 2D NMR, UV, IR, HRESIMS, and CD studies. These compounds represent the first members of a new biogenetic pathway for the isocoumarins nucleus involving shikimate derived A-ring coupling with a phenyl propanoid derivative.