A method for the acid-alkali extraction and preparative separation of triterpene acids from poria was established. The triterpene acids were enriched and separated into two fractions after extraction at the optimized pH value. The two fractions were subjected to high-speed counter-current chromatography for the preparative separation of triterpene acids, separately. As a result, dehydropachymic acid, pachymic acid, 3-epi-dehydropachymic acid, poricoic acid B, dehydrotumulosic acid, and 3-epi-dehydrotumulosic acid were obtained with purities of 94.1%, 96.2%, 93.5%, 85.9%, 80.1%, and 93.1%, respectively. The structures were identified by ESI-MS, 1 H NMR, and 13 C NMR.