Volatile oil composition of the leaves of Rhododendron anthopogon (Ericaceae) growing wild in alpine Western Himalaya was studied using different extraction techniques including SC-CO(2) extraction and hydrodistillation (HD). Results from different extraction methodologies were compared with headspace analysis (HS) and evaluated for the effectiveness of techniques in characterisation of various terpene categories and to assess their influence on the yield and composition of volatiles. Variability in constituents and in quantitative yields was observed. The results varied with different extraction methods. A total of 27 constituents in SC-CO(2) extraction, 31 in HD and 17 in HS analysis were identified. Constituents in SC-CO(2) and HD oils were identified by gas chromatography mass spectrometry analysis. SC-CO(2) extraction was carried out at 40°C and 140 bar pressure and the oil represented by major constituents as β-caryophyllene (5.96%), α-humulene (4.06%) and p-menthadiene-2,9-diol (7.28%); in HD, oil limonene (11.26%), β-caryophyllene (11.62%), α-humulene (7.22%), and E-nerolidol (5.83%) dominated the oil and in HS analysis, limonene (24.14%), γ-terpinene (40.73%), α-terpinene (4.92%), β-phellandrene (3.44%) and β-ocimene (7.15%) were present as major constituents.