Phlomis olivieri Benth is a valuable medicinal plant in the flora of Iran and can be collected in different parts of the country. To date, no comprehensive phytochemical research has been done on it in different parts of Iran. In this research, the essential oils of this medicinal plant were investigated in eight locations of western provinces of Iran. For this, aerial parts of the plant were collected in its natural habitats, dried under the shade condition (approximately 25°C), and then powdered. The essential oil was isolated by Clevenger apparatus and chemically analyzed by a Gas Chromatography (6890N)-Mass Spectroscopy (5973N) device in Payame Noor University (PNU), Hamedan, Iran. Except for some cases (EC, TNV, and K) there were no significant differences in the characteristics of the soil of the investigated areas. In the chemical structure of this plant, 17 and 11 constituents were identified in A1 and A2, 17 and 18 in B1 and B2, 17 and 15 in C1 and C2, and 21 and 15 in D1 and D2 locations of four western provinces in Iran. The results showed that caryophyllene (A1, A2, B1 and B2), 1H-cyclopenta [1, 3] cyclopropa [1, 2] benzene (C1), naphthalene, decahydro-4a–methyl (C2), estra-1, 3, 5(10)-trian-17a-ol (D1), and n-hexadecanoic acid (D2) were dominant constituents. Therefore, this valuable medicinal plant has diverse chemical constituents in the studied locations in Iran which should be considered from different aspects.