Two enantiomeric humulane sesquiterpenes, namely (+)‐alashanoid N (1a) and (−)‐alashanoid N (1b), along with two known analogs ((2R,3R,5R)‐2,3‐epoxy‐6,9‐humuladien‐5‐ol‐8‐one (2) and (2R,3S,5R)‐2,3‐epoxy‐6,9‐humuladien‐5‐ol‐8‐one (3)), were described from the peeled stems of a folk Mongolian herbal medicine Syringa pinnatifolia. Their structures were characterized based on UV, IR, NMR, and HR‐ESI‐MS data analyses, and the absolute configurations were determined by data analysis of X‐ray diffraction and quantum chemical calculations. (+/−)‐Alashanoid N showed inhibition against NO production in RAW 264.7 macrophage cells with IC50 values of 90.1 μM and 71.7 μM, and protective effect against oxygen‐glucose deprivation injury to H9c2 cells at a concentration of 20 μM and 5 μM, respectively.