The compositions of volatile components in the aerial parts of six Astragalus species, namely A. campylotrichus (Aca), A. chiwensis (Ach), A. lehmannianus (Ale), A. macronyx (Ama), A. mucidus (Amu) and A. sieversianus (Asi), were investigated using gas chromatograph-mass spectrometry (GC-MS) analysis. Ninety-seven metabolites were identified, accounting for 73.28, 87.03, 74.38, 87.93, 85.83, and 91.39% of Aca, Ach, Ale, Ama, Amu and Asi whole oils, respectively. Sylvestrene was the most predominant component in Asi, Amu and Ama, with highest concentration in Asi (64.64%). In addition, (E)-2-hexenal was present in a high percentage in both Ale and Ach (9.97 and 10.1%, respectively). GC-MS based metabolites were subjected to principal component analysis (PCA) and hierarchal cluster analysis (HCA) to explore the correlations between the six species. The PCA score plot displayed clear differentiation of all Astragalus species and a high correlation between the Amu and Ama species. The antioxidant activity was evaluated in vitro using various assays, phosphomolybdenum (PM), 2,2 diphenyl-1-picryl-hydrazyl-hydrate (DPPH), 2,2-azino bis (3-ethylbenzothiazoline-6-sulphonic acid) (ABTS), cupric reducing antioxidant capacity (CUPRAC), ferric reducing power (FRAP) and ferrous ion chelation (FIC) assays. In addition, the potential for the volatile samples to inhibit both acetyl/butyrylcholinesterases (AChE, BChE), α- amylase, α-glucosidase and tyrosinase was assessed. Most of the species showed considerable antioxidant potential in the performed assays. In the DPPH assay, Ama exhibited the maximum activity (24.12 ± 2.24 mg TE/g sample), and the volatiles from Amu exhibited the highest activity (91.54 mgTE/g oil) in the ABTS radical scavenging assay. The effect was more evident in both CUPRAC and FRAP assays, where both Ale and Ama showed the strongest activity in comparison with the other tested species (84.06, 80.28 mgTE/g oil for CUPRAC and 49.47, 49.02 mgTE/g oil for FRAP, respectively). Asi demonstrated the strongest AChE (4.55 mg GALAE/g oil) and BChE (3.61 mg GALAE/g oil) inhibitory effect. Furthermore, the best tyrosinase inhibitory potential was observed for Ale (138.42 mg KAE/g). Accordingly, Astragalus species can be utilized as promising natural sources for many medicinally important components that could be tested as drug candidates for treating illnesses such as Alzheimer’s disease, diabetes mellitus and oxidative stress-related diseases.