An endophytic isolate of Aspergillus fumigatus was obtained from the healthy stem of Cynodon dactylon. The fungus was identified on the basis of its morphology and aspects of its molecular biology. Volatile constituents were characterized from this fungus and analyzed by gas chromatography (GC) and gas chromatography/mass spectrometry (GC/MS). As a result, a total of twenty-two compounds represented all of the ligarine extract were characterized. Higher amounts of oil-based straight-chained alkyl ethyl esters and fatty acids were found to compose major volatile chemotype accounted for 42.44% and 35.05% of this organism, respectively. The main components was demonstrated to be 9,12-octadecadienoic acid, ethyl ester (16.96%); linoleic acid (16.48%); ethyl oleate (15.14%); n-hexadecanoic acid (9.13%); hexadecanoic acid, ethyl ester (7.80%). Some pharmaceutical components were discovered such as linoleic acid, linoleic acid ethyl ester, α- and γ-tocopherol, which could potentially be used in the field of medicine. Antioxidant activity of the extract was assessed by the free radical scavenging (DPPH).