The volatile compounds were extracted from the mycelia and fruiting bodies of the artificial culture of Ophiocordyceps longissima using simultaneous distillation and extraction (SDE) method. Their volatile components were analyzed using gas chromatography-mass spectrometry (GC-MS). The results showed that culture conditions had great influence on the content and number of volatile components; however, little impact on component classes was observed. The main volatile substances in mycelia were ketones, alcohols, alkenes, phenols and ethers, while alcohols, aldehydes, and phenols are main volatile compounds in fruiting bodies. Twenty compounds were detected in the mycelia liquid in which the content of 1-octene-3-alcohl (37.70%) was the highest. Six compounds were identified from the artificial culture of the fruiting bodies with the content of 1-octene-3-alcohl (51.93%) and butylated hydroxytoluene (38.37%) being relatively high. The compounds of 1-octen-3-ol and butylated hydroxytoluene are two common constituents in both artificial cultures and their contents were accounted for 51.66% and 90.30% of the total volatile components in mycelia and fruiting body, respectively.