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<i>Antrodia camphorata</i> (AC) is a precious medicinal mushroom native to Taiwan and famous for its excellent pharmacological activity. A ball mill assisted mechanochemical extraction method was applied in the extraction of triterpenoids from <i>Antrodia camphorata</i>. Compared with the ethanol hot thermal reflux method, mechanochemical-assisted extraction afforded an increased yield of triterpenoids to 1.82 &#177; 0.04% under conditions of mixing with 10 WT% NaHCO3, milling for 20 min, and extracting with water and chloroform. Triterpenoids from <i>Antrodia camphorata</i> extracted by the mechanochemical-assisted extraction method (TAEM) resulted in stronger pharmacological activity as compared to that extracted by ethanol (TAEE). HPLC and LC-MS/MS results showed that the mechanochemical method could extract triterpenoids which were barely extracted by ethanol extraction. The results of this study could provide valuable ideas and a basis for the application of the mechanochemical-assisted extraction method in the extraction of triterpenoids from AC.