Ackee (Blighia sapida K. D. Koenig) is an exotic fruit widely consumed in the Caribbean countries. While there is extensive research on the presence of hypoglycin A, other bioactive compounds have not been studied. We identified and quantified the changes in bioactive molecules (total phenol, ascorbic acid, hypoglycin A, squalene, D: A-Friedooleanan-7-ol, (7.alpha.), and oleic acid), antioxidant potential, and volatile compounds during two stages of ripe. A clear reduction in hypoglycin A, ascorbic acid, and total polyphenols during the maturation process were observed. On the contrary, oleic acid, squalene, and D: A-Friedooleanan-7-ol, (7.alpha.) contents increased about 12, 12, and 13 times, respectively with advancing maturity. These bioactive molecules were positively correlated with radical scavenging (DDPH and ABTS). Solid phase microextraction (SPME) and gas chromatography coupled mass spectrometry (GC/MS) analysis revealed more than 50 compounds with 3-penten-2-one and hexanal as the major compounds in the fully ripe stage. The results suggested that ripe ackee arilli could serve as an appreciable source of natural bioactive micro-constituents.