Sideritis congesta, an endemic plant to Turkey, is extensively consumed as energizing herbal tea and used as a remedy in folk medicine. This study was designed to comparatively evaluate the phytochemical composition and antioxidant potentials of different extracts (methanol, infusion) and fractions (chloroform, ethyl acetate, and remaining water) of S. congesta. Antioxidant potentials of the samples were evaluated by DPPH radical scavenging, FRAP, CUPRAC, and total antioxidant capacity tests. Total phenolic, phenolic acid, and flavonoid contents were also evaluated spectrophotometrically. Moreover, presence of twenty-two phenolic metabolites were affirmed by using LC-MS/MS in MRM scan mode and then the quantification of verbascoside, martynoside, and leucoseptoside A was performed by using HPTLC densitometry. EtOAc fraction contained the highest phenolic content and the antioxidant activity, as well as the highest verbascoside and martynoside contents followed by R-H2O fraction. Phytochemical studies on R-H2O fraction, yielded seven compounds, including a phenylethanoid glycoside, verbascoside (1), two flavonoids, stachyspinoside (2), isoscutellarein 7-O-(6‴-O-acetyl)-β-allopyranosyl-(1 → 2)-β-glucopyranoside (3), a phenolic acid chlorogenic acid (4), an iridoid glycoside ajugoside (5), and a monoterpenoid glucoside mixture betulalbuside A (6) and 1-hydroxylinaloyl 6-O-β-D-glucopyranoside (7). The molecular structures of the isolated compounds were determined by NMR and MS experiments. This is the first phytochemical study on the polar constituent of S. congesta and the first report of the isolation of compounds 2, 6 and 7 from the genus Sideritis L.