Roots of the Himalayan Peony (Paeonia emodi Royle) have been used as a traditional medicine for epilepsy since long back. In this study, hydrodistilled essential oil of the fresh roots of P. emodi, collected from western Himalaya was investigated using gas chromatography-flame ionization detector (GC-FID), gas chromatography-mass spectrometry (GC-MS), and nuclear magnetic resonance (NMR, 1H&13C). Altogether, twenty-four constituents, forming 97.4% of the total oil composition were identified. Major constituents of the essential oil were salicylaldehyde (85.5%), cis-myrtanal (4.9%), myrtenal (1.8%), trans-myrtanol (1.6%), and nopinone (1.4%). To the best of our knowledge, this is the first detailed report on P. emodi root essential oil composition.