Valerian contains about 0.2–2.8% volatile oil principally constituted of bornyl acetate and bornyl isovalerate. Other significant constituents of the oil are β-caryophyllene, bornyl formate, eugenyl isovalerate, isoeugenyl isovalerate, eugenol, cyclopentane sesquiterpenes—valeranone, valerenal, valerenic acid, and acetoxyvalerenic acid. Volatile oil composition is variable in different sub species of valerian. For example, V. edulis and V. wallichii lack valerenic acid. Japanese valerian has as much as 8% volatile oil, however, not similar to that of V. officinalis.

Valepotriates are another important group of constituents in Valerian species. First discovered from V. wallichii, these are non-glycosidic bicyclic iridoid monoterpene epoxy-iridoid esters. Ranging from 0.05–0.67% in different species, >90% of valpotriate content is made up of valtrate and isovaltrate. Smaller quantities of dihydrovaltrate, isovaleroxy-hydroxy dihydrovaltrate, 1-acevaltrate are also found. Valepotriates are unstable due to their epoxy structure and losses occur fairly rapidly on storage or due to improper drying conditions. Such undesirable processing may result in the formation of baldrinal, homobaldrinal and valtroxal as degradation products.

Quartenary alkaloids of about 0.05–0.1% have also been reported from the dried roots.

Nardostachys jatamansii (Syn: Nardostachys grandiflora) yields upto 2% volatile oil called spikenard oil, constituted of α-pinene, β-pinene, limonene, dihydroazulenes, α-gurjunene, β-gurjunene, seychelane, β-maaliene, nardol, nardostachnol apart form sesquiterpenes, spirojatamol, patchouli alcohol, nor seychelanone, α, β patchoulenes, jatamol A & B, jatamansic acid among others. Terpene coumarins angelicin, jatamansin, lignan and neo lignans such as (+)-hydroxypinoresinol and virolin and terpenoid ester nardostachysin are the other reported constituents of Jatamansii rhizomes.

Nardostachys jatamansii does not contain valepotriates.